Metallocenes and Methods Thereof

ABSTRACT

The present disclosure provides metallocene catalyst compounds including at least one —Si— containing linker, catalyst systems including such compounds, and uses thereof. Catalyst compounds of the present disclosure can be hafnium-containing compounds having one or more cyclopentadiene ligand(s) substituted with one or more silyl neopentyl groups and linked with at least one —Si-containing linker. In another class of embodiments, the present disclosure is directed to polymerization processes to produce polyolefin polymers from catalyst systems including one or more olefin polymerization catalysts, at least one activator, and an optional support.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Ser. No. 62/882,091, filed Aug. 2, 2019, herein incorporated by reference.

FIELD

The present disclosure relates to metallocene, catalyst systems comprising such compounds, and uses thereof. Furthermore, the present disclosure relates to metallocene including at least one —Si— containing linker. The present disclosure further relates to polymer compositions produced by the processes described herein.

BACKGROUND

Olefin polymerization catalysts are of great use in industry and polyolefins are widely used commercially because of their robust physical properties. Hence, there is interest in finding new catalyst systems that increase the marketing value of the catalyst and allow the production of polymers having improved properties. Polymer properties such as elasticity, and processability, are mainly controlled by the molecular weight, the molecular weight distribution, and the comonomer content of the polymers.

Polyolefins, such as polyethylene, typically have a comonomer (e.g., hexene), incorporated into the polyethylene backbone. These copolymers provide varying physical properties compared to polyethylene alone and are typically produced in a low pressure reactor, utilizing, for example, solution, slurry, or gas phase polymerization processes. Polymerization may take place in the presence of catalyst systems such as those using a Ziegler-Natta catalyst, a chromium based catalyst, or a metallocene catalyst.

There is a need for catalysts having high productivity and capable to produce tailored polyolefin materials for a variety of applications, for example, with tailored molecular weight (e.g., low Mw polymers for films; high Mw polymers for resins), tailored comonomer content, and narrow polydispersity indices. In particular, there is a need to develop new and improved catalyst systems for the polymerization of olefins, in order to achieve polymer properties, such as high melting point, and high molecular weight.

References for citing in an Information Disclosure Statement (37 CFR 1.97(h): Miyake, S. et al. (1998) “Synthesis, Molecular Structure, and Racemate-Meso Intercoversion for rac-(Me₂Si)₂{η⁵-C₅H-3-(CHMe₂)-5-Me}₂MCI₂(M+Ti and Zr),” Organometallics, v. 17(25), pp. 5528-5533; Licht, A. I., et al. (2003) “CH-Aktivierungsreaktionen an substituierten Zirconocenkomplexen undderen Verwendung in der katalytischen Ethylenpolymerisation,” J of Organometallic Chem., v. 684, pp. 91-104; Siedle, A. R., et al. (1995) “Stereochemical Nonrigidity in Metallocenium Ions,” J. of Organometallic Chem., v. 497, pp. 119-125; US 2018/0334517; US 2018/0237554; US 2018/0237558; US 2018/0237559; WO 2018/067259; KR 2015/066484; US 2018/0265605; KR 2015058054.

SUMMARY

The present disclosure relates to catalyst compounds represented by Formula (I):

wherein:

M is hafnium;

each of R¹, R², R³ and R⁴ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or R¹⁶-T²(R¹⁷)₃ where R¹⁶ is C₁ to C₄ hydrocarbyl, T² is group 13, 14, 15, or 16 element, and each R¹⁷ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl;

each of R⁵, R⁶, R⁷, R⁸, and R⁹ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸-T³(R¹⁹)₃ where R¹⁸ is C₁ to C₄ hydrocarbyl, T³ is group 13, 14, 15, or 16 element, and each R¹⁹ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl;

X¹ is a univalent anionic ligand;

each of R¹⁰ and R¹¹ is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, or R¹⁰ and R¹¹ join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent;

R¹² and R¹³ are hydrogen;

n is 1, 2, 3, 4, or 5;

T¹ is group 13, 14 (carbon excluded), 15, or 16 element; and

R¹⁴ and R¹⁵ are methyl.

In yet another embodiment, the present disclosure provides a catalyst system including an activator and a catalyst of the present disclosure.

In yet another embodiment, the present disclosure provides a catalyst system including an activator, a catalyst support, and a catalyst of the present disclosure.

In still another embodiment, the present disclosure provides a polymerization process including contacting one or more olefin monomers with a catalyst system including an activator and a catalyst of the present disclosure.

In still another embodiment, the present disclosure provides a polyolefin formed by a catalyst system and or method of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a GPC-4D spectrum of the polyethylene copolymer formed from Catalyst Compound 1 in Example 1.

FIG. 2 is a TREF graph of the polyethylene copolymer formed from Catalyst Compound 1 in Example 1.

DETAILED DESCRIPTION

The present disclosure provides catalyst compounds including at least one group 13, 14, 15, or 16 element-containing linker (e.g., —Si— linker), catalyst systems including such catalyst compounds, and uses thereof. In at least one embodiment, the present disclosure is directed to metallocene compounds, metallocene-based-catalyst systems, and their use in polymerization processes to produce polyolefin polymers, such as polyethylene polymers, polypropylene polymers, and copolymers. Catalyst compounds of the present disclosure can be hafnium-containing compounds having one or more cyclopentadiene ligand(s) substituted with one or more silyl neopentyl group and linked with at least one —Si-containing linker.

In another class of embodiments, the present disclosure is directed to polymerization processes to produce polyolefin polymers from catalyst systems including one or more olefin polymerization catalysts, at least one activator, and an optional support.

For example, the present disclosure is directed to a polymerization process to produce a polyethylene polymer, the process including contacting a catalyst system including one or more metallocene catalysts, at least one activator, and optionally at least one support, with ethylene and one or more C₃-C₁₀ alpha-olefin comonomers under polymerization conditions.

Catalysts, catalyst systems, and processes of the present disclosure can provide polyolefins at high Mw (e.g., 100,000 g/mol or greater), Mn values of 100,000 g/mol or greater, narrow PDI (e.g., about 1.5 to about 3), high Mz values (e.g., 500,000 g/mol or greater), MI values of from about 0.05 g/10 min to about 2.5 g/10 min, MIR values of about 12 to 100, such as 12 to 50, a g′_(vis) value of 0.97 or greater, and/or a broad orthogonal composition distribution. Alternatively, catalysts, catalyst systems, and processes of the present disclosure can provide polyolefins at low Mw (e.g., less than 100,000 g/mol), Mn values of less than 100,000 g/mol, narrow PDI (e.g., about 1.5 to about 3), and/or low Mz values (e.g., less than 500,000 g/mol), MI values of from about 0.05 g/10 min to about 2.5 g/10 min, MIR values of about 12 to 100, such as 12 to 50, a g′_(vis) value of 0.97 or greater, and a broad orthogonal composition distribution. Catalysts, catalyst systems, and processes of the present disclosure can provide polymers having a comonomer content from about 0.05 wt % to about 18 wt %.

For the purposes of the present disclosure, the numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News, v. 63(5), pg. 27 (1985). Therefore, a “group 4 metal” is an element from group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

The following abbreviations may be used herein: Me is methyl, Et is ethyl, Ph is phenyl, tBu is tertiary butyl, Cp is cyclopentadiene, Cp* is pentamethylcyclopentadienyl, PDI is polydispersity index, MAO is methylalumoxane, SMAO is supported methylalumoxane, NMR is nuclear magnetic resonance, THF is tetrahydrofuran, RPM is rotation per minute, MI is melt index, MIR is melt index ratio, BOCD is broad orthogonal composition distribution, MWD is molecular weight distribution, HMW is high molecular weight.

The specification describes hafnium-containing metal complexes. The term complex is used to describe molecules in which an ancillary ligand is coordinated to a central transition metal atom. The ligand is bulky and stably bonded to the transition metal so as to maintain its influence during use of the catalyst, such as polymerization. The ligand may be coordinated to the transition metal by covalent bond and or electron donation coordination or intermediate bonds. The transition metal complexes are generally subjected to activation to perform their polymerization or oligomerization function using an activator which, without being bound by theory, is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the transition metal.

As used herein, “olefin polymerization catalyst(s)” refers to any catalyst, such as an organometallic complex or compound that is capable of coordination polymerization addition where successive monomers are added in a monomer chain at the organometallic active center.

The terms “substituent,” “radical,” “group,” and “moiety” may be used interchangeably.

“Catalyst productivity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T×W) and expressed in units of gPgcat⁻¹ hr⁻¹. “Conversion” is the amount of monomer that is converted to polymer product, and is reported as mol % and is calculated based on the polymer yield and the amount of monomer fed into the reactor.

“BOCD” refers to a Broad Orthogonal Composition Distribution in which the comonomer of a copolymer is incorporated predominantly in the high molecular weight chains or species of a polyolefin polymer or composition. The distribution of the short chain branches can be measured, for example, using Temperature Raising Elution Fractionation (TREF) in connection with a Light Scattering (LS) detector to determine the weight average molecular weight of the molecules eluted from the TREF column at a given temperature. The combination of TREF and LS (TREF-LS) yields information about the breadth of the composition distribution and whether the comonomer content increases, decreases, or is uniform across the chains of different molecular weights of polymer chains. BOCD has been described, for example, in U.S. Pat. No. 8,378,043, Col. 3, line 34, bridging Col. 4, line 19, and 8,476,392, line 43, bridging Col. 16, line 54.

An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as including an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an “ethylene” content of 35 wt % to 55 wt %, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt % to 55 wt %, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. “Different” is used to refer to mer units and indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer including at least 50 mol % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer including at least 50 mol % propylene derived units, and so on. An “ethylene polymer” or “ethylene copolymer” is a polymer or copolymer including at least 50 mol % ethylene derived units, a “propylene polymer” or “propylene copolymer” is a polymer or copolymer including at least 50 mol % propylene derived units, and so on.

The term “alpha-olefin” refers to an olefin having a terminal carbon-to-carbon double bond in the structure thereof ((R″R′″)—C═CH₂, where R″ and R′″ can be independently hydrogen or any hydrocarbyl group; such as R″ is hydrogen and R′″ is an alkyl group). A “linear alpha-olefin” is an alpha-olefin defined in this paragraph wherein R″ is hydrogen, and R′″ is hydrogen or a linear alkyl group.

For the purposes of the present disclosure, ethylene shall be considered an alpha-olefin.

As used herein, and unless otherwise specified, the term “Cn” means hydrocarbon(s) having n carbon atom(s) per molecule, wherein n is a positive integer. The term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and or unsaturated), including mixtures of hydrocarbon compounds having different values of n. Likewise, a “C_(m)-C_(y)” group or compound refers to a group or compound including carbon atoms at a total number thereof from m to y. Thus, a C₁-C₅₀ alkyl group refers to an alkyl group including carbon atoms at a total number thereof from about 1 to about 50.

Unless otherwise indicated, (e.g., the definition of “substituted hydrocarbyl”, “substituted aromatic”, etc.), the term “substituted” means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, —(CH₂)q-SiR*₃, where q is 1 to 10 and each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

The term “substituted hydrocarbyl” means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one heteroatom (such as halogen, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e.g., —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, —(CH₂)q-SiR*₃, where q is 1 to 10 and each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring. The term “hydrocarbyl substituted phenyl” means a phenyl group having 1, 2, 3, 4 or 5 hydrogen groups replaced by a hydrocarbyl or substituted hydrocarbyl group. For example, the “hydrocarbyl substituted phenyl” group can be represented by the formula:

where each of R^(a), R^(b), R^(c), R^(d), and R^(e) can be independently selected from hydrogen, C₁-C₄₀ hydrocarbyl or C₁-C₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom-containing group (provided that at least one of R^(a), R^(b), R^(c), R^(d), and R^(e) is not H), or two or more of R^(a), R^(b), R^(c), R^(d), and R^(e) can be joined together to form a C₄-C₆₂ cyclic or polycyclic hydrocarbyl ring structure, or a combination thereof.

The term “substituted aromatic,” means an aromatic group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

The term “substituted phenyl,” mean a phenyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

The term “substituted naphthyl,” means a naphthyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

The term “substituted benzyl” means a benzyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group, such as a substituted benzyl group is represented by the formula:

where each of R^(a′), R^(b′), R^(c′), R^(d′), and R^(e′) and Z is independently selected from hydrogen, C₁-C₄₀ hydrocarbyl or C₁-C₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom-containing group (provided that at least one of R^(a′), R^(b′), R^(c′), R^(d′), and R^(e′) and Z is not H), or two or more of R^(a′), R^(b′), R^(c′), R^(d′), and R^(e′) and Z are joined together to form a C₄-C₆₂ cyclic or polycyclic ring structure, or a combination thereof.

The terms “alkoxy” and “alkoxide” mean an alkyl or aryl group bound to an oxygen atom, such as an alkyl ether or aryl ether group/radical connected to an oxygen atom and can include those where the alkyl/aryl group is a C₁ to C₁₀ hydrocarbyl. The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. Examples of suitable alkoxy radicals can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxyl.

The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals can include ethenyl, propenyl, allyl, 1,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, including their substituted analogues.

The terms “alkyl radical,” and “alkyl” are used interchangeably throughout this disclosure. For purposes of this disclosure, “alkyl radical” is defined to be C₁-C₁₀₀ alkyls that may be linear, branched, or cyclic. Examples of such radicals can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, including their substituted analogues. Substituted alkyl radicals are radicals in which at least one hydrogen atom of the alkyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*3, —PbR*₃, or —(CH₂)—SiR*₃, and each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

The term “aryl” or “aryl group” means an aromatic ring and the substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise, heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. As used herein, the term “aromatic” also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.

Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in the family. Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).

The term “ring atom” means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.

The terms “hydrocarbyl radical,” “hydrocarbyl group,” or “hydrocarbyl” may be used interchangeably and are defined to mean a group including hydrogen and carbon atoms only. For example, a hydrocarbyl can be a C₁-C₁₀₀ radical that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals may include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups, such as phenyl, benzyl naphthyl.

A “metallocene” catalyst compound is a transition metal catalyst compound having one, two or three, such as one or two, substituted or unsubstituted cyclopentadienyl ligands bound to the transition metal, such as a metallocene catalyst is an organometallic compound containing at least one π-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety).

The term “cyclopentadienyl”, also referred to as “Cp”, refers to a class of coordination complexes that are univalent anion derived from a hydride of a cyclopentadiene, which can form metallocene compounds with transition metals. Cp has 5 π electrons in the 5 out-of-plane p-orbitals on the C atoms.

The term “pentamethylcyclopentadienyl”, also referred to as Cp*, refers to a class of coordination complexes derived from cyclopentadiene. Cp* ligands are bulkier and more basic than unsubstituted Cp ligands, which results in distinctive properties. Without being bound by theory, it is believed that Cp* being more electron-rich than unsubstituted Cp, Cp* is a stronger donor and is less easily removed from the metal. Consequently its complexes may exhibit increased thermal stability. Its steric bulk may allow the isolation of complexes with otherwise fragile ligands. Its complexes also tend to be highly soluble in non-polar solvents.

Melt Index (MI), for example, is indicative of a polymer's molecular weight and the Melt Index Ratio (MIR) is indicative of the molecular weight distribution. A polymer that exhibits a higher MI has a shorter polymer chain length. As MIR increases, the molecular weight distribution (MWD) of the polymer broadens. A polymer that exhibits a narrower molecular weight distribution has a lower MIR.

“Linear polymer” means that the polymer has few, if any, long chain branches and has a branching index (g′_(vis)) value of about 0.967 or above, such as about 0.979 or above, such as about 0.98 or above. The branching index is determined by using a high temperature gel permeation chromatography equipped with three in-line detectors, a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer (GPC-4D).

Unless otherwise indicated, as used herein, “low comonomer content” is defined as a polyolefin having less than 8 wt % of comonomer based upon the total weight of the polyolefin. As used herein, “high comonomer content” is defined as a polyolefin having greater than or equal to 8 wt % of comonomer based upon the total weight of the polyolefin.

As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt % is weight percent, and mol % is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.

Unless otherwise indicated, as used herein, “high molecular weight” is defined as a number average molecular weight (Mn) value of 100,000 g/mol or more. “Low molecular weight” is defined as an Mn value of less than 100,000 g/mol.

Unless otherwise noted all melting points (Tm) are differential scanning calorimetry (DSC) first heat.

A “catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional coactivator, and an optional support material. The terms “catalyst compound”, “catalyst complex”, “transition metal complex”, “transition metal compound”, “precatalyst compound”, and “precatalyst complex” are used interchangeably. When “catalyst system” is used to describe such a pair before activation, it means the unactivated catalyst complex (precatalyst) together with an activator and, optionally, a coactivator. When it is used to describe such a pair after activation, it means the activated complex and the activator or other charge-balancing moiety. The transition metal compound may be neutral as in a precatalyst, or a charged species with a counter ion as in an activated catalyst system. For the purposes of the present disclosure and the claims thereto, when catalyst systems are described as including neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. A polymerization catalyst system is a catalyst system that can polymerize monomers to polymer. Furthermore, catalyst compounds and activators represented by formulae herein are intended to embrace both neutral and ionic forms of the catalyst compounds and activators.

In the description herein, the catalyst may be described as a catalyst, a catalyst precursor, a pre-catalyst compound, catalyst compound or a transition metal compound, and these terms are used interchangeably.

An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal ion. A “Lewis base” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion. Examples of Lewis bases include ethylether, trimethylamine, pyridine, tetrahydrofuran, dimethylsulfide, and triphenylphosphine. The term “heterocyclic Lewis base” refers to Lewis bases that are also heterocycles. Examples of heteroyclic Lewis bases include pyridine, imidazole, thiazole, and furan.

A scavenger is a compound that can be added to facilitate polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as coactivators. A coactivator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In at least one embodiment, a coactivator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound.

Non-coordinating anion (NCA) is defined to mean an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. A Lewis acid is defined to be a compound or element that can react with an electron donor to form a bond. An NCA coordinates weakly enough that a Lewis base, such as an olefin monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon.

The term “continuous” means a system that operates without interruption or cessation. For example a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.

A solution polymerization means a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization can be homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Suitable systems may be not turbid as described in Oliveira, J. V. (2000) “High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res., v. 39(12), pp. 4627-4633.

A bulk polymerization means a polymerization process in which the monomers and or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system contains less than 25 wt % of inert solvent or diluent, such as less than 10 wt %, such as less than 1 wt %, such as 0 wt %.

The BOCD Index may be defined as described in U.S. Pat. No. 9,290,593 ('593 Patent), which is fully incorporated herein by reference, by the following equation: BOCD Index=(Content of SCB at the high molecular weight side—Content of SCB at the low molecular weight side)/(Content of SCB at the low molecular weight side), wherein the “Content of SCB at the high molecular weight side” means the content of the SCB (the number of branches/1,000 carbon atoms) included in a polymer chain having a molecular weight of Mw of the polyolefin or more and 1.3×Mw or less, and the “Content of SCB at the low molecular weight side” means the content of the SCB (the number of branches/1,000 carbon atoms) included in a polymer chain having a molecular weight of 0.7×Mw of the polyolefin or more and less than Mw. The BOCD Index defined by the equation above may be in the range of 1 to 5, such as 2 to 4, such as 2 to 3.5. See, also, FIG. 1 and FIG. 2 of the '593 Patent (characterizing BOCD polymer structures using GPC-FTIR data).

The breadth of the composition distribution may be characterized by the T₇₅-T₂₅ value, wherein T₂₅ is the temperature at which 25% of the eluted polymer is obtained and T₇₅ is the temperature at which 75% of the eluted polymer is obtained in a TREF experiment as described herein. The composition distribution is further characterized by the F₈₀ value, which is the fraction of polymer that elutes below 80° C. in a TREF-LS experiment as described herein. A higher F₈₀ value indicates a higher fraction of comonomer in the polymer molecule. An orthogonal composition distribution is defined by a M₆₀/M₉₀ value that is greater than 1, wherein M₆₀ is the molecular weight of the polymer fraction that elutes at 60° C. in a TREF-LS experiment and M₉₀ is the molecular weight of the polymer fraction that elutes at 90° C. in a TREF-LS experiment as described herein.

Transition Metal Complexes

In at least one embodiment, the present disclosure relates to novel metallocene transition metal complexes, where the complexes include at least one cyclopentadienyl ligand with suitable combinations of substituents and linked with, for example, at least one group 13, 14 (carbon excluded), 15, or 16 element group.

In at least one embodiment, the present disclosure relates to novel bridged metallocene transition metal complexes, where the complexes include at least one cyclopentadienyl ligand with suitable combinations of substituents and linked with, for example, at least one —Si— group.

The linker can be characterized in that it has a —Si—Y— or —Ge—Y—, moiety, Y being unsubstituted hydrocarbyl or substituted hydrocarbyl, such as Y is C₁-C₁₀ hydrocarbyl.

In at least one embodiment, a catalyst compound is represented by Formula (I):

wherein:

M is hafnium;

each of R¹, R², R³ and R⁴ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or R¹⁶-T²(R¹⁷)₃ where R¹⁶ is C₁ to C₄ hydrocarbyl, T² is group 13, 14, 15, or 16 element, and each R¹⁷ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl (such as —R¹⁶—Si(R¹⁷)₃ where R¹⁶ is C₁ to C₄ hydrocarbyl, and each R¹⁷ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl);

each of R⁵, R⁶, R⁷, R⁸, and R⁹ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸-T³(R¹⁹)₃ where R¹⁸ is C₁ to C₄ hydrocarbyl, T³ is group 13, 14, 15, or 16 element, and each R¹⁹ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl (such as —R¹⁸—Si(R¹⁹)₃ where R¹⁸ is C₁ to C₄ hydrocarbyl, and each R¹⁹ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl);

X¹ is a univalent anionic ligand;

each of R¹⁰ and R¹¹ is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, or R¹⁰ and R¹¹ join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent;

R¹² and R¹³ are hydrogen;

n is 1, 2, 3, 4, or 5;

T¹ is group 13, 14 (carbon excluded), 15, or 16 element; and

R¹⁴ and R¹⁵ are independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl (such as independently C¹ to C¹⁰ substituted or unsubstituted hydrocarbyl, for example R¹⁴ and/or R¹⁵ are methyl).

T¹, T², and T³ can be independently a group 13, 14 (carbon excluded), 15, or 16 element, such as T¹, T², and T³ can be independently Si or Ge. In at least one embodiment, T¹ is Si. In at least one embodiment, T¹, T², and T³ are Si.

Furthermore, —((R¹⁴)(R¹⁵)T¹)- wherein T¹ can be Si, and R¹⁴ and R¹⁵ can be methyl. For example, —((R¹⁴)(R¹⁵)T^(L))- can be the linking group —(Me)₂Si—.

Each of R¹, R², R³ and R⁴ can be independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁶—Si(R¹⁷)₃ where R¹⁶ can be C₁ to C₄ hydrocarbyl, and each R¹⁷ can be independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl.

Each of R⁵, R⁶, R⁷, R⁸, and R⁹ can be independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸—Si(R¹⁹)₃ where R¹⁸ can be C₁ to C₄ hydrocarbyl, and each R¹⁹ can be independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl. At least one R¹⁹ may be C₁ to C₂₀ substituted or unsubstituted hydrocarbyl. At least one of R⁵, R⁶, R⁷, R⁸, and R⁹ can be —R¹⁸—Si(R¹⁹)₃ or —R¹⁸—C(R¹⁹)₃ where R¹⁸ can be C₁ to C₄ hydrocarbyl, and each R¹⁹ can be independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl.

Each of R¹⁰ and R¹¹ can be independently hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, or R¹⁰ and R¹¹ can join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent.

In at least one embodiment, at least one of R¹, R², R³ and R⁴ is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl or —R¹⁶—Si(R¹⁷)₃ where R¹⁶ is C₁ to C₄ hydrocarbyl, and each R¹⁷ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and at least one of R¹, R², R³ and R⁴ is hydrogen.

In at least one embodiment, each of R¹ and R² together do not form a ring and or each of R² and R³ together do not form a ring, or each of R³ and R⁴ together do not form a ring, or each of R⁴ and R⁵ together do not form a ring. In another embodiment, each of R⁵ and R⁶ together do not form a ring and or each of R⁶ and R⁷ together do not form a ring, or each of R⁷ and R⁸ together do not form a ring, or each of R⁸ and R⁹ together do not form a ring, or each of R⁹ and R⁵ together do not form a ring.

In at least one embodiment, R¹, R², R³ and R⁴ are hydrogen.

Furthermore, at least one of R⁵, R⁶, R⁷, R⁸, and R⁹ can be independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl or —R¹⁸—Si(R¹⁹)₃ where R¹⁸ can be C₁ to C₄ hydrocarbyl, and each R¹⁹ can be independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and each R⁵, R⁶, R⁷, R⁸, and R⁹ can be hydrogen. In at least one embodiment, one of R⁵, R⁶, R⁷, R⁸, and R⁹ is —R¹⁸—Si(R¹⁹)₃ where R¹⁸ is C₁ to C₄ hydrocarbyl, each R¹⁹ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and R⁵, R⁶, R⁷, R⁸, and R⁹ are hydrogen. In another embodiment, R⁵ is —R¹⁸—Si(R¹⁹)₃ where R¹⁸ is C₁ hydrocarbyl, and each R¹⁹ is independently C₁ to C₂₀ unsubstituted hydrocarbyl. In yet another embodiment, each R¹⁹ is methyl.

In at least one embodiment, R⁵, R⁶, R⁷, R⁸, and R⁹ are methyl such that the Cp ligand is a Cp* ligand.

Furthermore, n can be 1 to 5, such as n can be 1 to 3, for example n can be 1, 2, or 3. Also, q can be 1 to 5, such as q can be 1, 2, 3, 4, or 5. In at least one embodiment, n is 1 and q is 1.

R¹, R², R³, R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ can be hydrogen and R⁵ can be —R¹⁸—Si(R¹⁹)₃ where R¹⁸ can be C₁ hydrocarbyl, and each R¹⁹ can be independently C₁ to C₂₀ unsubstituted hydrocarbyl, such as R¹, R², R³, R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ can be hydrogen and R⁵ can be —R¹⁸—Si(R¹⁹)₃ where R¹⁸ can be —CH₂—, and each R¹⁹ can be methyl.

X¹ can be a univalent anionic ligand.

Exemplary groups suitable for X¹ may include 1,4-diphenyl, or 2,4-hexadiene, phenyl, or 1,4-dibenzyl. X¹ can be a C₁-C₃ alkyl or alkoxy group, a C₆-C₁₀ aryl or aryloxy group, a C₂-C₄ alkenyl group, a C₇-C₁₀ arylalkyl group, a C₇-C₁₂ alkylaryl group, or a halogen atom, such as chlorine.

In at least one embodiment, X¹ is selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

In at least one embodiment, the catalyst compound is one or more of:

In at least one embodiment, the catalyst compound represented by Formula (I) is:

In at least one embodiment, one catalyst compound is used, e.g., the catalyst compounds are not different. For purposes of the present disclosure, one metallocene catalyst compound is considered different from another if they differ by at least one atom. For example, “biscyclopentadienyl hafnium dichloride” is different from “(cyclopentadienyl)(2-methylcyclopentadienyl) hafnium dichloride” which is different from “(cyclopentadienyl)(2-methylcyclopentadienyl) zirconium dichloride.” Catalyst compounds that differ only by isomer are considered the same for purposes of the present disclosure unless otherwise noted, e.g., rac-tetramethyldisilyl-bis(trimethylsilylmethylcyclopentadienyl) hafnium dimethyl is considered to be the same as meso-tetramethyldisilyl-bis(trimethylsilylmethylcyclopentadienyl) hafnium dimethyl.

Methods to Prepare the Catalyst Compounds

In at least one embodiment, the catalyst compound represented by Formula (I) is formed from an intermediate compound represented by Formula (II) via an intramolecular cyclometalation of a —(C(R^(10′))(R^(11′))_(n)-T^(1′)((R^(14′))(R^(15′))(R^(20′)))— moiety included in at least one of the Cp ligands and M (e.g., Hf). The intermediate compound is represented by Formula (II):

wherein:

M′ is hafnium;

each of R^(1′), R^(2′), R^(3′) and R^(4′) is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or R^(16′)-T^(2′)(R^(17′))₃ where R^(16′) is C₁ to C₄ hydrocarbyl, T^(2′) is group 13, 14, 15, or 16 element, and each R^(17′) is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl (such as —R^(16′)—Si(R^(17′))₃ where R^(16′) is C₁ to C₄ hydrocarbyl, and each R^(17′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl);

each of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R^(18′)-T^(3′)(R^(19′))₃ where R^(18′) is C₁ to C₄ hydrocarbyl, T^(3′) is group 13, 14, 15, or 16 element, and each R^(19′) is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl (such as —R^(18′)—Si(R^(19′))₃ where R^(18′) is C₁ to C₄ hydrocarbyl, and each R^(19′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl);

each of X^(1′) and X^(2′) is independently a univalent anionic ligand;

each of R^(10∝) and R^(11′) is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, or R^(10′) and R^(11′) join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent;

n′ is 1, 2, 3, 4, or 5;

T^(1′) is group 13, 14 (carbon excluded), 15, or 16 element;

each of R^(14′) and R^(15′) is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl (such as C₁ to C₂₀ or C₁ to C₁₀) substituted or unsubstituted hydrocarbyl, for example R^(14′) and/or R^(15′) are methyl);

R^(20′) is C₁ or more substituted or unsubstituted hydrocarbyl (such as C₁ to C₄₀ or C₁ to C₁₀) substituted or unsubstituted hydrocarbyl, for example R^(20′) is methyl, or R^(14′), R^(15′) and/or R^(20′) are methyl). In some embodiments, when a polymer grows at the R^(20′), R^(20′) can be C₄₀ or more, alternately C₁₀₀ or more, or C₁₀₀₀ or more, or C_(10,000) or more, or C_(20,000) or more.

In at least one embodiment, M′ of the intermediate compound represented by Formula (II) is Hf.

T^(1′), T^(2′), and T^(3′) of the intermediate compound represented by Formula (II) may be independently a group 13, 14 (carbon excluded), 15, or 16 element, such as T^(1′), T^(2′), and T^(3′) are independently Si or Ge. In at least one embodiment, T^(1′), T^(2′), and T^(3′) are Si. In at least one embodiment, T^(1′) is Si.

In further embodiments, at least one of R^(1′), R^(2′), R^(3′) and R^(4′) of the intermediate compound represented by Formula (II) is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl or —R^(16′)—Si(R^(17′))₃ where R^(16′) is C₁ to C₄ hydrocarbyl, and each R^(17′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and at least one of R^(1′), R^(2′), R^(3′) and R^(4′) is hydrogen. For example, R^(1′), R^(2′), R^(3′) and R^(4′) can be hydrogen.

In other embodiments, at least one of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) of the intermediate compound represented by Formula (II) is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl or —R^(18′)—Si(R^(19′))₃ where R^(18′) is C₁ to C₄ hydrocarbyl, and each R^(19′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and at least one of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) is hydrogen. In at least one embodiment, one of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) of the intermediate compound represented by Formula (II) is —R^(18′)—Si(R^(19′))₃ where R^(18′) can be C₁ to C₄ hydrocarbyl, each R^(19′) can be independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and four of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) of the intermediate compound of Formula (II) are hydrogen. For example, R^(5′) of the intermediate compound of Formula (II) can be —R^(18′)—Si(R^(19′))₃ where R^(18′) can be C₁ hydrocarbyl, and each R^(19′) can be independently C₁ to C₂₀ unsubstituted hydrocarbyl. In at least one embodiment, each R^(19′) is methyl.

Furthermore, n′ can be 1 to 5, such as n′ can be 1 to 3. In at least one embodiment, n′ is 1. For example, n′ of the intermediate compound represented by Formula (II) can be 1, and R^(1′), R^(2′), R^(3′), R^(4′), R¹, R^(7′), R^(8′), R^(9′), R^(10′), and R^(11′) of the intermediate compound represented by Formula (II) can be hydrogen.

Each of X^(1′) and X^(2′) can be independently a univalent anionic ligand. Alternatively, X^(1′) and X^(2′) may also be joined together to form an alkanediyl group or a conjugated C₄-C₄₀ diene ligand which is coordinated to M′ in a metallocyclopentene fashion.

Exemplary groups suitable for X^(1′) and X^(2′) may include 1,4-diphenyl, or phenyl. X^(1′) and X^(2′) can be identical and can be a C₁-C₃ alkyl or alkoxy group, a C₆-C₁₀ aryl or aryloxy group, a C₂-C₄ alkenyl group, a C₇-C₁₀ arylalkyl group, a C₇-C₁₂ alkylaryl group, or a halogen atom, such as chlorine.

In at least one embodiment, each X^(1′) and X^(2′) of the intermediate compound represented by Formula (II) is independently selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

In one aspect, an advantage is provided in that the separation of meso from rac isomers is not performed after synthesis of the intermediate compounds of the present disclosure. In certain aspects, the meso isomer is formed in a ratio of 99.9:0.1 or greater than the rac isomer. Amounts of rac and meso isomers are determined by ¹H NMR spectroscopy, and further atom connectivity can be established by single crystal X-ray crystallography.

In at least one embodiment, one intermediate compound is used, e.g., the intermediate compounds are not different. For purposes of the present disclosure, one metallocene intermediate compound is considered different from another if they differ by at least one atom. For example, “biscyclopentadienyl hafnium dichloride” is different from “(cyclopentadienyl)(2-methylcyclopentadienyl) hafnium dichloride.” Intermediate compounds that differ only by isomer are considered the same for purposes of the present disclosure unless otherwise noted, e.g., rac-tetramethyldisilyl-bis(trimethylsilylmethylcyclopentadienyl) hafnium dimethyl is considered to be the same as meso-tetramethyldisilyl-bis(trimethylsilylmethylcyclopentadienyl) hafnium dimethyl.

Synthesis of Intermediate Compounds and Catalyst Compounds

The following is a process illustrating one way to prepare the catalyst compounds represented by Formula (I) described herein and further exemplified in the examples. Metallocenes of the present disclosure represented by Formula (I) can be synthesized where a deprotonation via a metal salt of alkyl anion (e.g., n-BuLi) can be performed to form a cyclopentadienide. A double deprotonation via an alkyl anion (e.g., n-BuLi) can be performed to form a dianion. The lithiation can be regioselective. The preparation of the catalyst compound of the present disclosure can include a reaction of the dianion with a metal halide (e.g., HfCl₄). An alkylation reaction of the metal halide (e.g., HfCl₄) can be performed with an alkyl anion (e.g., n-BuLi), or a Grignard reagent (e.g., BuMgBr), to form an intermediate compound represented by Formula (II) (e.g., Bis-(η⁵-trimethylsilylmethylcyclopentadienyl)hafnium dibutyl, (Me₃SiCH₂Cp)₂HfBu₂). Thermolysis reaction of the intermediate compound represented by Formula (II) (e.g., (Me₃SiCH₂Cp)₂HfBu₂) at a temperature of from about 70° C. to about 120° C. (e.g., 90° C.) can provide C—H activation of one of the alkyl moieties of —C(R^(10′))(R^(11′))T^(1′)((R^(14′))(R^(15′))(R^(20′)))— (e.g., —CH₂Si(CH₃)₃), which can be followed by a chelation of the C—H activated moiety (e.g., —CH₂Si(CH₃)₂—CH₂—) between the Hf and Cp. Without being bound by theory, the C—H activation of the alkyl moiety (e.g., —CH₃) may occur through at least one of X^(1′) or X^(2′) elimination. For example, elimination of X^(1′) or X² may occur via β-hydride elimination (e.g., when X^(1′) and X^(2′) are butyl, X^(1′) or X^(2′) may eliminate as butene for example), which can generate hydrogen.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeably.

The catalyst systems described herein may comprise a catalyst complex as described above and an activator such as alumoxane or a non-coordinating anion and may be formed by combining the catalyst components described herein with activators in any manner known from the literature including combining them with supports, such as silica. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). Catalyst systems of the present disclosure may have one or more activators and one, two or more catalyst components. Activators are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral metal compound to a catalytically active metal compound cation. Non-limiting activators, for example, may include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Suitable activators may include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, 6-bound, metal ligand making the metal compound cationic and providing a charge-balancing non-coordinating or weakly coordinating anion, e.g., a non-coordinating anion.

In at least one embodiment, the catalyst system includes an activator and the catalyst compound of Formula (I).

Alumoxane Activators

Alumoxane activators are utilized as activators in the catalyst systems described herein. Alumoxanes are generally oligomeric compounds containing —Al(R^(a′″))—O— sub-units, where R^(a′″) is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, such as when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be suitable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Pat. No. 5,041,584, which is incorporated by reference herein). Another useful alumoxane is solid polymethylaluminoxane as described in U.S. Pat. Nos. 9,340,630, 8,404,880, and 8,975,209, which are incorporated by reference herein.

When the activator is an alumoxane (modified or unmodified), at least one embodiment select the maximum amount of activator at up to a 5,000-fold molar excess Al/M over the catalyst compound (per metal catalytic site). The minimum activator-to-catalyst-compound can be a 1:1 molar ratio. Alternate ranges may include from 1:1 to 500:1, alternately from 1:1 to 200:1, alternately from 1:1 to 100:1, or alternately from 1:1 to 50:1. In an alternate embodiment, little or no alumoxane is used in the polymerization processes described herein. For example, alumoxane can be present at zero mol %, alternately the alumoxane can be present at a molar ratio of aluminum to catalyst compound transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

Ionizing/Non-Coordinating Anion Activators

The term “non-coordinating anion” (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a Lewis base. “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization. Suitable ionizing activators may include an NCA, such as a compatible NCA.

It is within the scope of the present disclosure to use an ionizing activator, neutral or ionic. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. For descriptions of suitable activators please see U.S. Pat. Nos. 8,658,556 and 6,211,105.

The catalyst systems of the present disclosure can include at least one non-coordinating anion (NCA) activator. In at least one embodiment, boron containing NCA activators represented by the formula below can be used:

Z_(d) ⁺(A^(d−))

where: Z is (L-H) or a reducible Lewis acid; L is a Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A^(d−) is a boron containing non-coordinating anion having the charge d−; d is 1, 2, or 3.

The cation component, Z_(d) ⁺ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand transition metal catalyst precursor, resulting in a cationic transition metal species.

The activating cation Z_(d) ⁺ may also be a moiety such as silver, tropylium, carbeniums, ferroceniums and mixtures, such as carbeniums and ferroceniums. Z_(d) ⁺ can be triphenyl carbenium. Reducible Lewis acids can be a triaryl carbenium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl), such as the reducible Lewis acids “Z” may include those represented by the formula: (Ph₃C), where Ph is a substituted or unsubstituted phenyl, such as substituted with C₁ to C₄₀ hydrocarbyls or substituted a C₁ to C₄₀ hydrocarbyls, such as C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics, such as Z is a triphenylcarbenium.

When Z_(d) ⁺ is the activating cation (L-H)_(d) ⁺, it can be a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, such as ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, dioctadecylmethylamine, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.

The anion component A^(d−) includes those having the formula [M″^(k+)Q_(n)]^(d−) where k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (such as 1, 2, 3, or 4); n-k=d; M″ is an element selected from Group 13 of the Periodic Table of the Elements, such as boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Each Q can be a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, such as each Q is a fluorinated aryl group, and such as each Q is a pentafluoryl aryl group. Examples of suitable A^(d−) also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.

Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst are the compounds described as activators in U.S. Pat. No. 8,658,556, which is incorporated by reference herein.

The ionic stoichiometric activator Z_(d) ⁺ (A^(d−)) can be one or more of N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate.

Bulky activators are also useful herein as NCAs. “Bulky activator” as used herein refers to anionic activators represented by the formula:

where:

each R^(A) is independently a halide, such as a fluoride;

Ar is substituted or unsubstituted aryl group (such as a substituted or unsubstituted phenyl), such as substituted with C₁ to C₄₀ hydrocarbyls, such as C₁ to C₂₀ alkyls or aromatics;

each R^(B) is independently a halide, a C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si-R^(D), where R^(D) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (such as R^(B) is a fluoride or a perfluorinated phenyl group);

each R^(C) is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula —O—Si—R^(D), where R^(D) is a C₁ to C₂₀ hydrocarbyl or hydrocarbylsilyl group (such as R^(D) is a fluoride or a C₆ perfluorinated aromatic hydrocarbyl group); where R^(B) and R^(C) can form one or more saturated or unsaturated, substituted or unsubstituted rings (such as R^(B) and R^(C) form a perfluorinated phenyl ring);

L is a Lewis base; (L-H)⁺ is a Bronsted acid; d is 1, 2, or 3;

where the anion has a molecular weight of greater than 1,020 g/mol; and

where at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic Å, alternately greater than 300 cubic Å, or alternately greater than 500 cubic Å.

For example, (Ar₃C)_(d) ⁺ can be (Ph₃C)_(d) ⁺, where Ph is a substituted or unsubstituted phenyl, such as substituted with C₁ to C₄₀ hydrocarbyls or substituted C₁ to C₄₀ hydrocarbyls, such as C₁ to C₂₀ alkyls or aromatics or substituted C₁ to C₂₀ alkyls or aromatics.

“Molecular volume” is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.

Molecular volume may be calculated as reported in Girolami, G. S. (1994) “A Simple “Back of the Envelope” Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, v. 71(11), pp. 962-964, which is incorporated by reference herein. Molecular volume (MV), in units of cubic Å, is calculated using the formula: MV=8.3V_(S), where V_(S) is the scaled volume. V_(S) is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V_(S) is decreased by 7.5% per fused ring.

Element Relative Volume H 1 1^(st) short period, Li to F 2 2^(nd) short period, Na to Cl 4 1^(st) long period, K to Br 5 2^(nd) long period, Rb to I 7.5 3^(rd) long period, Cs to Bi 9

For a list of suitable bulky activators please see U.S. Pat. No. 8,658,556, which is incorporated by reference herein.

In another embodiment, one or more of the NCA activators is chosen from the activators described in U.S. Pat. No. 6,211,105.

In a at least one embodiment, the activator is selected from one or more of a triaryl carbenium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In another embodiment, the activator is selected from one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl, propyl, n-butyl, sec-butyl, or t-butyl).

Suitable activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio may be about a 1:1 molar ratio. Alternate ranges include from 0.1:1 to 100:1, alternately from 0.5:1 to 200:1, alternately from 1:1 to 500:1, alternately from 1:1 to 1000:1. Suitable ranges can be from 0.5:1 to 10:1, such as 1:1 to 5:1.

It is also within the scope of the present disclosure that the catalyst compounds can be combined with combinations of alumoxanes and NCA's (see for example, U.S. Pat. Nos. 5,153,157; 5,453,410; EP 0573120 B1; WO 1994/007928; and WO 1995/014044 which discuss the use of an alumoxane in combination with an ionizing activator).

Useful chain transfer agents can be hydrogen, alkylalumoxanes, a compound represented by the formula AlR₃, ZnR₂ (where each R is, independently, a C₁-C₈ aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

Furthermore, a catalyst system of the present disclosure may include a metal hydrocarbenyl chain transfer agent represented by the formula:

Al(R′)_(3-v)(R″)_(v)

where each R′ can be independently a C₁-C₃₀ hydrocarbyl group, and or each R″, can be independently a C₄-C₂₀ hydrocarbenyl group having an end-vinyl group; and v can be from 0.1 to 3.

Optional Scavengers or Coactivators

In addition to these activator compounds, scavengers or coactivators may be used. Aluminum alkyl or alumoxane compounds which may be utilized as scavengers or coactivators may include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, methylalumoxane (MAO), modified methylalumoxane (MMAO), MMAO-3A, and diethyl zinc.

Optional Support Materials

In embodiments herein, the catalyst system may include an inert support material. The supported material can be a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or another organic or inorganic support material, or mixtures thereof.

The support material can be an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in catalyst systems herein may include groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina can be magnesia, titania, zirconia. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania. In at least one embodiment, the support material is selected from Al₂O₃, ZrO₂, SiO₂, SiO₂/Al₂O₃, SiO₂/TiO₂, silica clay, silicon oxide/clay, or mixtures thereof.

The support material, such as an inorganic oxide, can have a surface area of from about 10 m²/g to about 700 m²/g, pore volume of from about 0.1 cm³/g to about 4.0 cm³/g and average particle size of from about 5 μm to about 500 μm. The surface area of the support material can be of from about 50 m²/g to about 500 m²/g, pore volume of from about 0.5 cm³/g to about 3.5 cm³/g and average particle size of from about 10 μm to about 200 μm. For example, the surface area of the support material can be from about 100 m²/g to about 400 m²/g, pore volume from about 0.8 cm³/g to about 3.0 cm³/g and average particle size can be from about 5 μm to about 100 μm. The average pore size of the support material useful in the present disclosure can be of from 10 Å to 1,000 Å, such as 50 Å to about 500 Å, and such as 75 Å to about 350 Å. In at least one embodiment, the support material is a high surface area, amorphous silica (surface area=300 m²/gm; pore volume of 1.65 cm³/gm). For example, suitable silicas can be the silicas marketed under the tradenames of DAVISON™ 952 or DAVISON™ 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments, DAVISON™ 948 is used. Alternatively, a silica can be ES-70™ silica (PQ Corporation, Malvern, Pa.) that has been calcined, for example (such as at 875° C.).

The support material should be dry, that is, free of absorbed water. Drying of the support material can be effected by heating or calcining at about 100° C. to about 1,000° C., such as at least about 600° C. When the support material is silica, it is heated to at least 200° C., such as about 200° C. to about 850° C., and such as at about 600° C.; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst including at least one catalyst compound and an activator.

The support material, having reactive surface groups, such as hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In at least one embodiment, the slurry of the support material is first contacted with the activator for a period of time of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The solution of the catalyst compound is then contacted with the isolated support/activator. In at least one embodiment, the supported catalyst system is generated in situ. In alternate embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The slurry of the supported catalyst compound is then contacted with the activator solution.

The mixture of the catalyst, activator and support is heated from about 0° C. to about 70° C., such as from about 23° C. to about 60° C., such as at room temperature. Contact times can be from about 0.5 hours to about 24 hours, such as from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactants used herein, e.g., the activator and the catalyst compound, are at least partially soluble and which are liquid at reaction temperatures. Non-polar solvents can be alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.

In at least one embodiment, the support material is a supported methylalumoxane, which is a methylalumoxane treated silica (see, for example, SMAO-ES70-875 as described in the Experimental section below).

Polymerization Processes

The present disclosure relates to polymerization processes where monomer (e.g., ethylene; propylene), and optionally comonomer, are contacted with a catalyst system including an activator and at least one catalyst compound, as described above. The catalyst compound and activator may be combined in any order. The catalyst compound and activator may be combined prior to contacting with the monomer. Alternatively the catalyst compound and activator may be introduced into the polymerization reactor separately, wherein they subsequently react to form the active catalyst.

Monomers may include substituted or unsubstituted C₂ to C₄₀ alpha olefins, such as C₂ to C₂₀ alpha olefins, such as C₂ to C₁₂ alpha olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof. In at least one embodiment, the monomer includes ethylene and an optional comonomer including one or more C₃ to C₄₀ olefins, such as C₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and or one or more functional groups. In another embodiment, the monomer includes propylene and an optional comonomer including one or more ethylene or C₄ to C₄₀ olefins, such as C₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. The C₄ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₄ to C₄₀ cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers may include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, ethylidenenorbornene, vinylnorbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and their respective homologs and derivatives, such as norbornene, norbornadiene, and dicyclopentadiene.

Polymerization processes of the present disclosure can be carried out in any suitable manner. Any suitable suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes can be used. A bulk homogeneous process can be used. Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts found with the monomer; e.g., propane in propylene). In another embodiment, the process is a slurry process. As used herein, the term “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt % of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization may include non-coordinating, inert liquids. Examples of diluents/solvents for polymerization may include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof, cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™); perhalogenated hydrocarbons, such as perfluorinated C₄ to C₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents may also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. In at least one embodiment, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, such as aromatics are present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as less than 0 wt % based upon the weight of the solvents.

In at least one embodiment, the feed concentration of the monomers and comonomers for the polymerization is 60 vol % solvent or less, such as 40 vol % or less, such as 20 vol % or less, based on the total volume of the feedstream. In at least one embodiment, the polymerization is run in a bulk process.

Polymerizations can be run at any temperature and or pressure suitable to obtain the desired polymers. Suitable temperatures and or pressures include a temperature of from about 0° C. to about 300° C., such as about 20° C. to about 200° C., such as about 35° C. to about 160° C., such as from about 80° C. to about 160° C., such as from about 90° C. to about 140° C. Polymerizations can be run at a pressure of from about 0.1 MPa to about 25 MPa, such as from about 0.45 MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa.

In a suitable polymerization, the run time of the reaction can be up to 300 minutes, such as from about 5 minutes to 250 minutes, such as from about 10 minutes to 120 minutes, such as from about 20 minutes to 90 minutes, such as from about 30 minutes to 60 minutes. In a continuous process the run time may be the average residence time of the reactor. In at least one embodiment, the run time of the reaction is from about 5 minutes to about 25 minutes.

In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), such as from 0.01 psig to 25 psig (0.07 kPa to 172 kPa), such as from 0.1 psig to 10 psig (0.7 kPa to 70 kPa).

In at least one embodiment, little or no alumoxane is used in the process to produce the polymers. For example, alumoxane can be present at zero mol %, alternately the alumoxane can be present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

In at least one embodiment, the polymerization: 1) is conducted at temperatures of 0° C. to 300° C. (such as 25° C. to 250° C., such as 80° C. to 160° C., such as 100° C. to 140° C.); 2) is conducted at a pressure of atmospheric pressure to 10 MPa (such as 0.35 MPa to 10 MPa, such as from 0.45 MPa to 6 MPa, such as from 0.5 MPa to 4 MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as where aromatics are present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as at 0 wt % based upon the weight of the solvents); 4) wherein the catalyst system used in the polymerization comprises less than 0.5 mol %, such as 0 mol % alumoxane, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1; 5) the polymerization occurs in one reaction zone; 6) optionally scavengers (such as trialkyl aluminum compounds) are absent (e.g., present at zero mol %, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1); and 7) optionally hydrogen is present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa) (such as from 0.01 psig to 25 psig (0.07 kPa to 172 kPa), such as 0.1 psig to 10 psig (0.7 kPa to 70 kPa)). In at least one embodiment, the catalyst system used in the polymerization includes no more than one catalyst compound. A “reaction zone” also referred to as a “polymerization zone” is a vessel where polymerization takes place, for example a stirred-tank reactor or a loop reactor. When multiple reactors are used in a continuous polymerization process, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in a batch polymerization process, each polymerization stage is considered as a separate polymerization zone. In at least one embodiment, the polymerization occurs in one reaction zone. Room temperature is 23° C. unless otherwise noted.

In at least one embodiment, the present disclosure provides a process for the production of an ethylene based polymer including: polymerizing ethylene by contacting the ethylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form an ethylene based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 5 psig to about 300 psig, such as from about 10 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 20 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig).

In another embodiment, the present disclosure provides a process for the production of propylene based polymer including: polymerizing propylene by contacting the propylene with the catalyst system of the present disclosure described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.5 MPa to 1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form a propylene based polymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig).

In another embodiment, the present disclosure provides a process for the production of an ethylene alpha-olefin copolymer including: polymerizing ethylene and at least one C₃-C₂₀ alpha-olefin (e.g., hexene) by contacting the ethylene and the at least one C₃-C₂₀ alpha-olefin (e.g., hexene) with a catalyst system described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form an ethylene alpha-olefin copolymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig), alternatively from about 150 psig to about 300 psig (e.g., 200 psig).

In at least one embodiment, a process for the production of an ethylene alpha-olefin copolymer comprises: polymerizing ethylene and at least one C₃-C₂₀ alpha-olefin by contacting the ethylene and the at least one C₃-C₂₀ alpha-olefin with catalyst system described above in at least one gas phase reactor at a reactor pressure of from 0.7 bar to 70 bar (e.g., 17 bar) and a reactor temperature of from 20° C. to 150° C., such as from 50° C. to 120° C., such as from 70° C. to 110° C. (e.g., 85° C.) to form an ethylene alpha-olefin copolymer.

In another embodiment, the present disclosure provides a process for the production of a propylene alpha-olefin copolymer including: polymerizing propylene and at least one ethylene and or at least one C₄-C₂₀ alpha-olefin by contacting the propylene and the at least one ethylene and or at least one C₃-C₂₀ alpha-olefin with a catalyst system described above in one or more continuous stirred tank reactors or loop reactors, in series or in parallel, at a reactor pressure of from 0.05 MPa to 1,500 MPa and a reactor temperature of from 30° C. to 230° C. to form an ethylene alpha-olefin copolymer. In at least one embodiment, hydrogen is present in the polymerization reactor at a partial pressure of from about 10 psig to about 300 psig, such as from about 20 psig to about 250 psig, such as from about 30 psig to about 200 psig, such as from about 40 psig to about 150 psig, such as from about 50 psig to about 100 psig (e.g., 75 psig), alternatively from about 150 psig to about 300 psig (e.g., 200 psig).

In at least one embodiment, the conversion of olefin monomer is at least 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, such as 20% or more, such as 30% or more, such as 50% or more, such as 80% or more.

In at least one embodiment, little or no alumoxane is used in the process to produce the polymers. For example, alumoxane is present at zero mol %, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500:1, such as less than 300:1, such as less than 100:1, such as less than 1:1.

In at least one embodiment, little or no scavenger is used in the process to produce the ethylene polymer. For example, scavenger (such as tri alkyl aluminum) is present at zero mol %, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1.

Other additives may also be used in the polymerization, as desired, such as one or more scavengers, hydrogen, aluminum alkyls, or chain transfer agents (such as alkylalumoxanes, a compound represented by the formula AlR₃ or ZnR₂ (where each R is, independently, a C₁-C₅ aliphatic radical, such as methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof).

Solution Polymerization

A solution polymerization is a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization is typically homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Such systems are not turbid as described in Oliveira, J. V. (2000) “High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems,” Ind. Eng. Chem. Res., v. 39(12), pp. 4627-4633. Solution polymerization may involve polymerization in a continuous reactor in which the polymer formed, the starting monomer and catalyst materials supplied are agitated to reduce or avoid concentration gradients and in which the monomer acts as a diluent or solvent or in which a hydrocarbon is used as a diluent or solvent. Suitable processes can operate at temperatures from about 0° C. to about 250° C., such as from about 50° C. to about 170° C., such as from about 80° C. to about 150° C., such as from about 100° C. to about 140° C., and or at pressures of about 0.1 MPa or more, such as 2 MPa or more. The upper pressure limit is not critically constrained but can be about 200 MPa or less, such as 120 MPa or less, such as 30 MPa or less. Temperature control in the reactor can generally be obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds can also be used. The purity, type, and amount of solvent can be optimized for the maximum catalyst productivity for a particular type of polymerization. The solvent can be also introduced as a catalyst carrier. The solvent can be introduced as a gas phase or as a liquid phase depending on the pressure and temperature. Advantageously, the solvent can be kept in the liquid phase and introduced as a liquid. Solvent can be introduced in the feed to the polymerization reactors.

A process described herein can be a solution polymerization process that may be performed in a batchwise fashion (e.g., batch; semi-batch) or in a continuous process. Suitable reactors may include tank, loop, and tube designs. In at least one embodiment, the process is performed in a continuous fashion and dual loop reactors in a series configuration are used. In at least one embodiment, the process is performed in a continuous fashion and dual continuous stirred-tank reactors (CSTRs) in a series configuration are used. Furthermore, the process can be performed in a continuous fashion and a tube reactor can be used. In another embodiment, the process is performed in a continuous fashion and one loop reactor and one CSTR are used in a series configuration. The process can also be performed in a batchwise fashion and a single stirred tank reactor can be used.

Polyolefin Products

The present disclosure relates to compositions of matter produced by the methods described herein.

In at least one embodiment, a process described herein produces C₂ to C₂₀ olefin homopolymers (e.g., polyethylene; polypropylene), or C₂ to C₂₀ olefin copolymers (e.g., ethylene-octene, ethylene-propylene) and or propylene-alpha-olefin copolymers, such as C₃ to C₂₀ copolymers (such as propylene-hexene copolymers or propylene-octene copolymers) having comonomer incorporation (such as C₆ wt %) of from about 0.05 wt % to about 25 wt %, such as from about 0.05 wt % to about 18 wt %.

In at least one embodiment, a polymer of the present disclosure has an Mw from about 100,000 g/mol to about 3,000,000 g/mol, such as from about 175,000 g/mol to about 2,500,000 g/mol, such as from about 500,000 g/mol to about 2,250,000 g/mol, such as from about 800,000 g/mol to about 1,500,000 g/mol. Alternatively, a polymer of the present disclosure has an Mw of less than 100,000 g/mol, such as from about 500 g/mol to about 90,000 g/mol, such as from about 2,500 g/mol to about 75,000 g/mol, such as from about 5,000 g/mol to about 50,000 g/mol.

In at least one embodiment, a polymer of the present disclosure has an Mz from about 500,000 g/mol to about 15,000,000 g/mol, such as from about 750,000 g/mol to about 12,500,000 g/mol, such as from about 1,000,000 g/mol to about 10,000,000 g/mol, such as from about 1,500,000 g/mol to about 8,000,000 g/mol, such as from about 2,000,000 g/mol to about 7,000,000 g/mol. Alternatively, a polymer of the present disclosure has an Mz of less than 500,000 g/mol, such as from about 500 g/mol to about 450,000 g/mol, such as from about 5,000 g/mol to about 250,000 g/mol, such as from about 10,000 g/mol to about 100,000 g/mol, such as from about 5,000 g/mol to about 250,000 g/mol, such as from about 25,000 g/mol to about 75,000 g/mol.

In at least one embodiment, a polymer of the present disclosure has an Mn from about 100,000 g/mol to about 2,000,000 g/mol, such as from about 175,000 g/mol to about 1,500,000 g/mol, such as from about 250,000 g/mol to about 1,250,000 g/mol, such as from about 350,000 g/mol to about 1,000,000 g/mol. Alternatively, a polymer of the present disclosure has an Mn of less than 100,000 g/mol, such as from about 500 g/mol to about 90,000 g/mol, such as from about 2,500 g/mol to about 75,000 g/mol, such as from about 5,000 g/mol to about 50,000 g/mol.

In at least one embodiment, a polymer of the present disclosure has an Mw/Mn (PDI) value from about 1 to about 5, such as from about 2 to about 4, such as from about 2.5 to about 3.5, such as from about 3 to about 3.5, alternatively from about 1.5 to about 2.5.

Likewise, the process of the present disclosure produces olefin polymers, such as polyethylene and polypropylene homopolymers and copolymers. In at least one embodiment, the polymers produced herein are homopolymers of ethylene or copolymers of ethylene having, for example, from about 0.05 wt % to about 25 wt % (alternately from about 0.5 wt % to about 20 wt %, alternately from about 1 wt % to about 15 wt %, such as from about 1 wt % to about 10 wt %, alternatively from about 8 wt % to about 13 wt %) of one or more C₃ to C₂₀ olefin comonomer (such as C₃ to C₁₂ alpha-olefin, such as propylene, butene, hexene, octene, decene, dodecene, such as propylene, butene, hexene, octene). In at least one embodiment, the monomer is ethylene and the comonomer is hexene, such as from about 0.05 wt % to about 18 wt % hexene, such as from about 0.1 wt % to about 16 wt % hexene, such as from about 2 wt % to about 14 wt % hexene, alternately about 8 wt % to about 14 wt % based on the weight of the polymer.

In at least one embodiment, the polymers produced herein are homopolymers of propylene or are copolymers of propylene having, for example, from about 0.05 wt % to about 25 wt % (alternately from about 0.5 wt % to about 20 wt %, alternately from about 1 wt % to about 15 wt %, such as from about 1 wt % to about 10 wt %, such as from about 3 wt % to about 10 wt %) of one or more of C₂ or C₄ to C₂₀ olefin comonomer (such as ethylene or C₄ to C₁₂ alpha-olefin, such as ethylene, butene, hexene, octene, decene, dodecene, such as ethylene, butene, hexene, octene). In at least one embodiment, the monomer is propylene and the comonomer is hexene, such as from about 0.05 wt % to about 18 wt % hexene, such as from about 0.1 wt % to about 16 wt % hexene, such as from about 2 wt % to about 14 wt % hexene, alternately about 8 wt % to about 14 wt %, based on the weight of the polymer. In a further embodiment, the polymers produced herein have a broad orthogonal composition distribution.

In at least one embodiment, the polymers of the present disclosure have an melt index (I2) of from about 0.05 g/10 min to about 2.5 g/10 min, such as from about 0.1 g/10 min to about 2 g/10 min, such as from about 0.5 g/10 min to about 1.5 g/10 min.

In at least one embodiment, the polymers of the present disclosure have a g′_(vis) of greater than 0.9, such as greater than 0.92, such as greater than 0.95, such as greater than 0.96.

In at least one embodiment, the polymers have a MIR value greater than 12, such as from 12 to 100, such as 12 to 50, such as from 14 to 45, such as from 16 to 40, such as from 18 to 35.

In at least one embodiment, the polymers produced herein have an Mw of about 100,000 g/mol to about 5,000,000 g/mol, an Mn from about 100,000 g/mol to about 2,000,000 g/mol, an Mz from about 500,000 g/mol to about 15,000,000 g/mol, and or an Mw/Mn (PDI) of about 1.2 to 10, such as 1 to 5 (e.g., about 2.5).

In at least one embodiment, a polymer produced herein has a unimodal or multimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC). By “unimodal” is meant that the GPC trace has one peak or inflection point. By “multimodal” is meant that the GPC trace has at least two peaks or inflection points. An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versus). In at least one embodiment, a polymer produced herein has a bimodal molecular weight distribution as determined by Gel Permeation Chromatography (GPC).

GPC 4-D

For purposes of the claims, and unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content and the branching index (g′) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm⁻¹ to about 3,000 cm⁻¹ (representing saturated C—H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) including ˜300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of ˜1 mL/min and a nominal injection volume of ˜200 μL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ˜145° C. A given amount of sample can be weighed and sealed in a standard vial with ˜10 μL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with ˜8 mL added TCB solvent at ˜160° C. with continuous shaking. The sample solution concentration can be from ˜0.2 to −2 mg/ml, with lower concentrations used for higher molecular weight samples.

The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation: c=αI, where α is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm/mole. The MW at each elution volume is calculated with following equation:

${\log M} = {\frac{\log\left( {K_{PS}/K} \right)}{\alpha + 1} + {\frac{\alpha_{PS} + 1}{\alpha + 1}\log M_{PS}}}$

where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, α_(PS)=0.67 and K_(PS)=0.000175, α and K for other materials are as calculated in the published in literature (see for example, Sun, T. et al. (2001) “Effect of Short Chain Branching on the Coil Dimensions of Polyolefins in Dilute Solution” Macromolecules, v. 34, pp. 6812-6820), except that for purposes of this present disclosure and claims thereto, α=0.695+(0.01*(wt. fraction propylene)) and K=0.000579-(0.0003502*(wt. fraction propylene)) for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 for linear butene polymers, a is 0.695 and K is 0.000579*(1-0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, a is 0.695 and K is 0.000579*(1-0.0075*w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and a is 0.695 and K is 0.000579*(1-0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mol, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted.

The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH₂ and CH₃ channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH₃/1,000TC) as a function of molecular weight. The short-chain branch (SCB) content per 1,000TC (SCB/1,000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH₃/1,000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which f is 0.3, 0.4, 0.6, 0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively:

w2 = f * SCB/1, 000TC

The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH₃ and CH₂ channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained

${{Bulk}{IR}{ratio}} = {\frac{{Area}{of}{CH}_{3}{signal}{within}{integration}{limits}}{{Area}{of}{CH}_{2}{signal}{within}{integration}{limits}}.}$

Then the same calibration of the CH₃ and CH₂ signal ratio, as mentioned previously in obtaining the CH3/1,000TC as a function of molecular weight, is applied to obtain the bulk CH3/1,000TC. A bulk methyl chain ends per 1,000TC (bulk CH3 end/1,000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range according to the following equations:

w2b = f * bulkCH3/1, 000TCbulkSCB/1, 000TC = bulkCH3/1, 000TC − bulkCH3end/1, 000TC

where bulk SCB/1,000TC is converted to bulk w2 in the same manner as described above.

The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972):

$\frac{K_{o}c}{\Delta{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}{c.}}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A₂ is the second virial coefficient, P(θ) is the form factor for a monodisperse random coil, and K_(O) is the optical constant for the system:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$

where N_(A) is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 145° C. and λ=665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048 ml/mg and A₂=0.0015; for analyzing ethylene-butene copolymers, dn/dc=0.1048*(1-0.00126*w2) ml/mg and A₂=0.0015 where w2 is weight percent butene comonomer.

A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, η_(S), for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]=η_(S)/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M=K_(PS)M^(α) ^(PS) ⁺¹/[η], where α_(ps) is 0.67 and K_(ps) is 0.000175.

The branching index (g′_(vis)) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [η]_(avg), of the sample is calculated by:

${\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}},$

where the summations are over the chromatographic slices, i, between the integration limits. The branching index g′_(vis) is defined as

${g_{vis}^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{KM_{v}^{\alpha}}},$

where M_(V) is the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and a are for the reference linear polymer, which are, for purposes of this present disclosure and claims thereto, as described above. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted. Calculation of the w2b values is as discussed above.

In at least one embodiment the polymer produced has a composition distribution breadth index (CDBI) of 50% or more, such as 60% or more, such as 70% or more. CDBI is a measure of the composition distribution of monomer within the polymer chains and is measured by the procedure described in PCT publication WO 1993/003093, published Feb. 18, 1993, specifically columns 7 and 8 as well as in Wild, L. et al. (1982) “Determination of Branching Distributions in Polyethylene and Ethylene Copolymers,” J. Poly. Sci., Poly. Phys. Ed., v. 20, pp. 441-455 and U.S. Pat. No. 5,008,204, including that fractions having a weight average molecular weight (Mw) below 15,000 g/mol are ignored when determining CDBI.

Blends

In another embodiment, the polymer (such as the polyethylene or polypropylene) produced herein is combined with one or more additional polymers prior to being formed into a film, molded part or other article. Other useful polymers include polyethylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and or butene, and or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and or polyisobutylene.

In at least one embodiment, the polymer (such as the polyethylene or polypropylene) is present in the above blends, at from 10 wt % to 99 wt %, based upon the weight of the polymers in the blend, such as 20 wt % to 95 wt %, such as at least 30 wt % to 90 wt %, such as at least 40 wt % to 90 wt %, such as at least 50 wt % to 90 wt %, such as at least 60 wt % to 90 wt %, such as at least 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of the present disclosure with one or more polymers (as described above), by connecting reactors together in series to make reactor blends or by using more than one catalyst in the same reactor to produce multiple species of polymer. The polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, such as by dry blending the individual components and subsequently melt mixing in a mixer, or by mixing the components together directly in a mixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabender internal mixer, or a single or twin-screw extruder, which may include a compounding extruder and a side-arm extruder used directly downstream of a polymerization process, which may include blending powders or pellets of the resins at the hopper of the film extruder. Additionally, additives may be included in the blend, in one or more components of the blend, and or in a product formed from the blend, such as a film, as desired. Such additives are well known in the art, and can include, for example: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites (e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives; tackifiers, such as polybutenes, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glycerol stearates, and hydrogenated rosins; UV stabilizers; heat stabilizers; anti-blocking agents; release agents; anti-static agents; pigments; colorants; dyes; waxes; silica; fillers; talc.

Films

Any of the foregoing polymers, such as the foregoing polypropylenes or blends thereof, may be used in a variety of end-use applications. Such applications include, for example, mono- or multi-layer blown, extruded, and or shrink films. These films may be formed by any number of well-known extrusion or coextrusion techniques, such as a blown bubble film processing technique, wherein the composition can be extruded in a molten state through an annular die and then expanded to form a uni-axial or biaxial orientation melt prior to being cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films may be subsequently unoriented, uniaxially oriented, or biaxially oriented to the same or different extents. One or more of the layers of the film may be oriented in the transverse and or longitudinal directions to the same or different extents. The uniaxially orientation can be accomplished using suitable cold drawing or hot drawing methods. Biaxial orientation can be accomplished using tenter frame equipment or a double bubble processes and may occur before or after the individual layers are brought together. For example, a polyethylene layer can be extrusion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. For example, the films can be oriented in the Machine Direction (MD) at a ratio of up to 15, such as from about 5 to about 7, and in the Transverse Direction (TD) at a ratio of up to 15, such as from about 7 to about 9. However, in another embodiment the film is oriented to the same extent in both the MD and TD directions.

The films may vary in thickness depending on the intended application; however, films of a thickness from 1 μm to 50 μm can be suitable. Films intended for packaging can be from 10 μm to 50 μm thick. The thickness of the sealing layer can be from 0.2 μm to 50 μm. There may be a sealing layer on both the inner and outer surfaces of the film or the sealing layer may be present on only the inner or the outer surface.

In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, flame treatment, or microwave. In at least one embodiment, one or both of the surface layers is modified by corona treatment.

Embodiments Listing

The present disclosure provides, among others, the following embodiments, each of which may be considered as optionally including any alternate embodiments.

Clause 1. A catalyst compound represented by Formula (I):

wherein:

M is hafnium;

each of R¹, R², R³ and R⁴ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or R¹⁶-T²(R¹⁷)₃ wherein R¹⁶ is C₁ to C₄ hydrocarbyl, T² is group 13, 14, 15, or 16 element, and each R¹⁷ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl (such as —R¹⁶—Si(R¹⁷)₃ wherein R¹⁶ is C₁ to C₄ hydrocarbyl, and each R¹⁷ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl);

each of R⁵, R⁶, R⁷, R⁸, and R⁹ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸-T³(R¹⁹)₃ wherein R¹⁸ is C₁ to C₄ hydrocarbyl, T³ is group 13, 14, 15, or 16 element, and each R¹⁹ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl (such as —R¹⁸—Si(R¹⁹)₃ wherein R¹⁸ is C₁ to C₄ hydrocarbyl, and each R¹⁹ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl);

X¹ is a univalent anionic ligand;

each of R¹⁰ and R¹¹ is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, or R¹⁰ and R¹¹ join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent;

R¹² and R¹³ are hydrogen;

n is 1, 2, 3, 4, or 5;

T¹ is group 13, 14 (carbon excluded), 15, or 16 element; and

R¹⁴ and R¹⁵ are independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl (such as independently C¹ to C¹⁰ substituted or unsubstituted hydrocarbyl, for example R^(14′) and or R^(15′) are methyl).

Clause 2. The catalyst compound of clause 1, wherein T¹ is Si. Clause 3. The catalyst compound of clauses 1 or 2, wherein n is 1 to 3. Clause 4. The catalyst compound of any of clauses 1 to 3, wherein n is 1. Clause 5. The catalyst compound of any of clauses 1 to 4, wherein each of R¹, R², R³ and R⁴ is independently hydrogen or C₁ to C₄₀ substituted or unsubstituted hydrocarbyl. Clause 6. The catalyst compound of any of clauses 1 to 5, wherein R¹, R², R³ and R⁴ are hydrogen. Clause 7. The catalyst compound of any of clauses 1 to 6, wherein each of R⁵, R⁶, R⁷, R⁸, and R⁹ is independently hydrogen, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸—Si(R¹⁹)₃ wherein R¹⁸ is C₁ to C₄ hydrocarbyl, and each R¹⁹ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl. Clause 8. The catalyst compound of any of clauses 1 to 7, wherein one of R⁵, R⁶, R⁷, R⁸, and R⁹ is —R¹⁸—Si(R¹⁹)₃ where R¹⁸ is C₁ to C₄ hydrocarbyl, each R¹⁹ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and four of R⁵, R⁶, R⁷, R⁸, and R⁹ are hydrogen. Clause 9. The catalyst compound of clause 7 or 8, wherein each R¹⁹ is independently C₁ to C₅ unsubstituted hydrocarbyl. Clause 10. The catalyst compound of any of clauses 1 to 9, wherein R¹⁸ is C₁ and each R¹⁹ is methyl. Clause 11. The catalyst compound of any of clauses 1 to 10, wherein n is 1, and R¹, R², R³, R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are hydrogen. Clause 12. The catalyst compound of any of clauses 1 to 11, wherein X¹ is selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Clause 13. The catalyst compound of any of clauses 1 to 12, wherein X¹ is butyl. Clause 14. The catalyst compound of clause 1, wherein the catalyst compound is one or more of:

Clause 15. The catalyst compound of clause 14, wherein the catalyst compound is selected from:

Clause 16. A catalyst system comprising an activator and the catalyst compound of any of clauses 1 to 15. Clause 17. The catalyst system of any of clauses 1 to 16, further comprising a support material. Clause 18. The catalyst system of any of clauses 1 to 17, wherein the support material is selected from Al₂O₃, ZrO₂, SiO₂, SiO₂/Al₂O₃, SiO₂/TiO₂, silica clay, silicon oxide/clay, or mixtures thereof. Clause 19. The catalyst system of any of clauses 16 to 18, wherein the activator comprises a non-coordinating anion activator. Clause 20. The catalyst system of clause 19, wherein the activator is represented by the formula:

(Z)_(d) ⁺(A^(d−))

wherein Z is (L-H) or a reducible Lewis Acid, L is an Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^(d−) is a non-coordinating anion having the charge d−; and d is an integer from 1 to 3. Clause 21. The catalyst system of clause 19, wherein the activator is represented by the formula:

(Z)_(d) ⁺(A^(d−))

wherein A^(d−) is a non-coordinating anion having the charge d−; d is an integer from 1 to 3, and Z is a reducible Lewis acid represented by the formula: (Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, a C₁ to C₄₀ hydrocarbyl, or a substituted C₁ to C₄₀ hydrocarbyl. Clause 22. The catalyst system of clause 19, wherein the activator is one or more of: N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluoronaphthyl)borate, tropillium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylphosphonium tetrakis(perfluoronaphthyl)borate, triethylsilylium tetrakis(perfluoronaphthyl)borate, benzene(diazonium) tetrakis(perfluoronaphthyl)borate, trimethylammonium tetrakis(perfluorobiphenyl)borate, triethylammonium tetrakis(perfluorobiphenyl)borate, tripropylammonium tetrakis(perfluorobiphenyl)borate, tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate, tri(t-butyl)ammonium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(perfluorobiphenyl)borate, tropillium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylphosphonium tetrakis(perfluorobiphenyl)borate, triethylsilylium tetrakis(perfluorobiphenyl)borate, benzene(diazonium) tetrakis(perfluorobiphenyl)borate, [4-t-butyl-PhNMe₂H][(C₆F₃(C₆F₅)₂)₄B], trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, tropillium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate, triethylsilylium tetraphenylborate, benzene(diazonium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, tropillium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, triethylsilylium tetrakis(pentafluorophenyl)borate, benzene(diazonium) tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate, tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, benzene(diazonium) tetrakis-(2,3,4,6-tetrafluorophenyl)borate, trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tri(t-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, benzene(diazonium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium, tetrakis(pentafluorophenyl)borate, 4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, and triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). Clause 23. The catalyst system of clause 16, further comprising a metal hydrocarbenyl chain transfer agent represented by the formula:

Al(R′)_(3-v)(R″)_(v)

wherein each R′ independently is a C₁-C₃₀ hydrocarbyl group; each R″, independently, is a C₄-C₂₀ hydrocarbenyl group having an end-vinyl group; and v is from 0.1 to 3. Clause 24. The catalyst system of clause 16, wherein the activator comprises an alkylalumoxane. Clause 25. The catalyst system of clause 24, wherein the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal of 100:1 or more. Clause 26. A process for the production of an ethylene alpha-olefin copolymer comprising: polymerizing ethylene and at least one C₃-C₂₀ alpha-olefin by contacting the ethylene and the at least one C₃-C₂₀ alpha-olefin with a catalyst system of any of clauses 16 to 25 in at least one gas phase reactor at a reactor pressure of from 0.7 bar to 70 bar and a reactor temperature of from 20° C. to 150° C. to form an ethylene alpha-olefin copolymer. Clause 27. An ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one C₃-C₂₀ alpha-olefin, and a catalyst system of any of clauses 16 to 25 in at least one gas-phase reactor, the copolymer having an Mw value of from 50,000 to 5,000,000, an Mn value of from 100,000 to 2,000,000, an Mz value of from 500,000 to 10,000,000, an Mw/Mn value of from 1.2 to 10, an MI of from about 0.05 g/10 min to about 2.5 g/10 min, a MIR value from 12 to 100, a g′_(vis) of greater than 0.9, and a comonomer content of from 0.05 wt % to 18 wt %. Clause 28. An ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one C₃-C₂₀ alpha-olefin, and a catalyst system of any of clauses 16 to 25 in at least one gas-phase reactor, the copolymer having an Mw value of from 500 to 100,000, an Mn value of from 500 to 100,000, an Mz value of from 500 to 500,000, an Mw/Mn value of from 1.2 to 10, an MI of from about 0.05 g/10 min to about 2.5 g/10 min, a MIR value from 12 to 50, a g′_(vis) of greater than 0.9, and a comonomer content of from 0.05 wt % to 18 wt %. Clause 29. The ethylene alpha-olefin copolymer of any of clauses 27 or 28, wherein the copolymer has a broad orthogonal composition distribution. Clause 30. The ethylene alpha-olefin copolymer of any of clauses 27 or 28, wherein the copolymer has a bimodal molecular weight distribution as determined by Gel Permeation Chromatography. Clause 31. An intermediate compound represented by Formula (II):

wherein.

M′ is hafnium;

each of R^(1′), R^(2′), R^(3′) and R^(4′) is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or R^(16′)-T^(2′)(R^(17′))₃ wherein R^(16′) is C₁ to C₄ hydrocarbyl, T^(2′) is group 13, 14, 15, or 16 element, and each R^(17′) is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl (such as —R^(16′)—Si(R^(17′))₃ wherein R^(16′) is C₁ to C₄ hydrocarbyl, and each R^(17′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl);

each of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R^(18′)—Si(R^(19′))₃ wherein R^(18′) is C₁ to C₄ hydrocarbyl, T^(3′) is group 13, 14, 15, or 16 element, and each R^(19′) is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl (such as —R^(18′)—Si(R^(19′))₃ wherein R^(18′) is C₁ to C₄ hydrocarbyl, and each R^(19′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl);

each of X^(1′) and X^(2′) is independently a univalent anionic ligand;

each of R^(10′) and R^(11′) is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl or substituted hydrocarbyl, or R^(10′) and R^(11′) join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent;

n′ is 1, 2, 3, 4, or 5;

T^(1′) is group 13, 14 (carbon excluded), 15, or 16 element;

each of R^(14′) and R^(15′), is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl (such as independently C₁ to C₁₀ substituted or unsubstituted hydrocarbyl, for example R^(14′) and/or R^(15′) are methyl); and

R^(20′) is independently C₁ or more substituted or unsubstituted hydrocarbyl (such as C₁ to C₄₀ or C₁ to C₁₀ substituted or unsubstituted hydrocarbyl, for example R^(20′) is methyl, or R^(14′), R^(15′) and/or R^(20′) are methyl).

Clause 32. The intermediate compound of clause 31, wherein T^(1′) is Si. Clause 33. The intermediate compound of clause 32, wherein n′ is 1 to 3. Clause 34. The intermediate compound of clause 33, wherein n′ is 1. Clause 35. The intermediate compound of clause 31, wherein at least one of R^(1′), R^(2′), R^(3′) and R^(4′) is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl or —R^(16′)—Si(R^(17′))₃ wherein R^(16′) is C₁ to C₄ hydrocarbyl, and each R^(17′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and at least one of R¹, R^(2′), R^(3′) and R^(4′) is hydrogen. Clause 36. The intermediate compound of clause 35, wherein R^(1′), R^(2′), R^(3′), and R^(4′) are hydrogen. Clause 37. The intermediate compound of clause 31, wherein at least one of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl or —R^(18′)-Si(R^(19′))₃ wherein R^(18′) is C₁ to C₄ hydrocarbyl, and each R^(19′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and at least one of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) is hydrogen. Clause 38. The intermediate compound of clause 37, wherein one of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) is —R^(18′)—Si(R^(19′))₃ wherein R^(18′) is C₁ to C₄ hydrocarbyl, each R^(19′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and four of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) are hydrogen. Clause 39. The intermediate compound of clause 37 or 38, wherein R^(5′) is —R^(18′)—Si(R^(19′))₃ wherein R^(18′) is C₁ hydrocarbyl, and each R^(19′) is independently C₁ to C₂₀ unsubstituted hydrocarbyl. Clause 40. The intermediate compound of clause 39, wherein each R^(19′) is methyl. Clause 41. The intermediate compound of clause 31, wherein n′ is 1 and R^(1′), R^(2′), R^(3′), R^(4′), R^(6′), R^(7′), R^(8′), R^(9′), R^(10′), and R^(11′) are hydrogen. Clause 42. The intermediate compound of any of clauses 31 to 41, wherein each of X^(1′) and X^(2′) is independently selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Clause 43. The intermediate compound of clause 42, wherein each of X^(1′) and X^(2′) is butyl. Clause 44. A process comprising:

heating at a temperature of from about 70° C. to about 120° C. for a time of from about 1 hour to about 72 hours an intermediate compound represented by Formula (II):

wherein:

M′ is hafnium;

each of R^(1′), R^(2′), R^(3′) and R^(4′) is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R^(16′)-T^(2′)(R^(17′))₃ wherein R^(16′) is C₁ to C₄ hydrocarbyl, T^(2′) is group 13, 14, 15, or 16 element, and each R^(17′) is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl;

each of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R^(18′)-T^(3′)(R^(19′))₃ wherein R^(18′) is C₁ to C₄ hydrocarbyl, T^(3′) is group 13, 14, 15, or 16 element, and each R^(19′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl;

each of X^(1′) and X^(2′) is independently a univalent anionic ligand;

each of R^(10′) and R^(11′) is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl or substituted hydrocarbyl, or R^(10′) and R^(11′) join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent;

n′ is 1, 2, 3, 4, or 5;

T^(1′) is group 13, 14 (carbon excluded), 15, or 16 element; and

each of R^(14′) and R^(15′) is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl;

R^(20′) is independently C₁ or more substituted or unsubstituted hydrocarbyl; and obtaining a catalyst compound represented by Formula (I):

wherein:

M is a hafnium;

each of R¹, R², R³ and R⁴ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or R¹⁶-T²(R¹⁷)₃ wherein R¹⁶ is C₁ to C₄ hydrocarbyl, T² is group 13, 14, 15, or 16 element, and each R¹⁷ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl;

each of R⁵, R⁶, R⁷, R⁸, and R⁹ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸-T³(R¹⁹)₃ wherein R¹⁸ is C₁ to C₄ hydrocarbyl, T³ is group 13, 14, 15, or 16 element, and each R¹⁹ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl;

X¹ is a univalent anionic ligand;

each of R¹⁰ and R¹¹ is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, or R¹⁰ and R¹¹ join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent;

R¹² and R¹³ are hydrogen;

n is 1, 2, 3, 4, or 5;

T¹ is group 13, 14 (carbon excluded), 15, or 16 element; and

R¹⁴ and R¹⁵ are independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl.

Clause 45. The process of clause 44, wherein the heating comprises heating the intermediate compound represented by Formula (II) at a temperature of from about 85° C. to about 95° C. for a time of from about 30 hours to about 40 hours.

Experimental Characterization GPC 4-D

For purposes of the claims, and unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content and the branching index (g′) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm⁻¹ to about 3,000 cm⁻¹ (representing saturated C—H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) including ˜300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of ˜1 mL/min and a nominal injection volume of ˜200 μL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ˜145° C. A given amount of sample can be weighed and sealed in a standard vial with ˜10 μL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with ˜8 mL added TCB solvent at ˜160° C. with continuous shaking. The sample solution concentration can be from ˜0.2 to ˜2 mg/ml, with lower concentrations used for higher molecular weight samples.

The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation: c=αI, where α is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to 10M gm/mole. The MW at each elution volume is calculated with following equation:

${\log M} = {\frac{\log\left( {K_{PS}/K} \right)}{\alpha + 1} + {\frac{\alpha_{PS} + 1}{\alpha + 1}\log M_{PS}}}$

where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, α_(PS)=0.67 and K_(PS)=0.000175, a and K for other materials are as calculated in the published in literature (see for example, Sun, T. et al. (2001) “Effect of Short Chain Branching on the Coil Dimensions of Polyolefins in Dilute Solutions,” Macromolecules, v. 34, pp. 6812-6820), except that for purposes of this present disclosure and claims thereto, α=0.695+(0.01*(wt. fraction propylene)) and K=0.000579-(0.0003502*(wt. fraction propylene)) for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 and K=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 for linear butene polymers, a is 0.695 and K is 0.000579*(1-0.0087*w2b+0.000018*(w2b){circumflex over ( )}2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, a is 0.695 and K is 0.000579*(1-0.0075*w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and a is 0.695 and K is 0.000579*(1-0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mol, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted.

The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH₂ and CH₃ channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1,000 total carbons (CH₃/1,000TC) as a function of molecular weight. The short-chain branch (SCB) content per 1,000TC (SCB/1,000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH₃/1,000TC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which f is 0.3, 0.4, 0.6, 0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively:

w2 = f * SCB/1, 000TC.

The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH₃ and CH₂ channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained

${{Bulk}{IR}{ratio}} = {\frac{{Area}{of}{CH}_{3}{signal}{within}{integration}{limits}}{{Area}{of}{CH}_{2}{signal}{within}{integration}{limits}}.}$

Then the same calibration of the CH₃ and CH₂ signal ratio, as mentioned previously in obtaining the CH₃/1,000TC as a function of molecular weight, is applied to obtain the bulk CH₃/1,000TC. A bulk methyl chain ends per 1,000TC (bulk CH₃ end/1,000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range according to the following equations:

w2b = f * bulkCH3/1, 000TCbulkSCB/1, 000TC = bulkCH3/1, 000TC − bulkCH3end/1, 000TC

where bulk SCB/1,000TC is converted to bulk w2 in the same manner as described above.

The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, M. B., Ed.; Academic Press, 1972):

$\frac{K_{o}c}{\Delta{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the IR5 analysis, A₂ is the second virial coefficient, P(θ) is the form factor for a monodisperse random coil, and K_(O) is the optical constant for the system:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{dn}/{dc}} \right)}^{2}}{\lambda^{4}N_{A}}$

where N_(A) is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n=1.500 for TCB at 145° C. and λ=665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048 ml/mg and A₂=0.0015; for analyzing ethylene-butene copolymers, dn/dc=0.1048*(1-0.00126*w2) ml/mg and A₂=0.0015 where w2 is weight percent butene comonomer.

A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, fs, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the equation [η]=η_(S)/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as M=K_(PS)M^(α) ^(PS) ⁺¹/[η], where α_(ps) is 0.67 and K_(ps) is 0.000175.

The branching index (g′_(vis)) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromatographic slices, i, between the integration limits. The branching index g′_(vis) is defined as

${g_{vis}^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{KM_{v}^{\alpha}}},$

where M_(V) is the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and α are for the reference linear polymer, which are, for purposes of this present disclosure and claims thereto, as described above. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted. Calculation of the w2b values is as discussed above.

¹H NMR: ¹H NMR data was collected at room temperature in a 5 mm probe using a Varian spectrometer with a ¹H frequency of at least 400 MHz. Data was recorded using a maximum pulse width of 45° C., 8 seconds between pulses and signal averaging 120 transients.

Gel Permeation Chromatography (GPC) High temperature size exclusion chromatography was performed using an automated “Rapid GPC” system as described in U.S. Pat. Nos. 6,491,816; 6,491,823; 6,475,391; 6,461,515; 6,436,292; 6,406,632; 6,175,409; 6,454,947; 6,260,407; and 6,294,388; each of which is incorporated by reference. Molecular weights (weight average molecular weight (Mw) and number average molecular weight (Mn)) and molecular weight distribution (MWD=Mw/Mn), which is also sometimes referred to as the polydispersity (PDI) of the polymer, were measured by Gel Permeation Chromatography using a Symyx Technology GPC equipped with evaporative light scattering detector and calibrated using polystyrene standards (Polymer Laboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between 5,000 and 3,390,000). Samples (250 μL of a polymer solution in TCB were injected into the system) were run at an eluent flow rate of 2.0 mL/minute (135° C. sample temperatures, 165° C. oven/columns) using three Polymer Laboratories: PLgel 10 μm Mixed-B 300×7.5 mm columns in series. No column spreading corrections were employed. Numerical analyses were performed using Epoch® software available from Symyx Technologies or Automation Studio software available from Freeslate. The molecular weights obtained are relative to linear polystyrene standards and are reported in g/mol.

Differential Scanning Calorimetry (DSC) measurements were performed on a TA-Q100 instrument to determine the melting point (Tm) of the polymers. Samples were pre-annealed at 220° C. for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220° C. at a rate of 100° C./min and then cooled at a rate of 50° C./min. Melting points were collected during the heating period.

FT-IR— The weight percent of comonomer (hexene) incorporated in polymers was determined by rapid FT-IR spectroscopy on a Bruker Equinox 55+ IR in reflection mode. Samples were prepared in a thin film format by evaporative deposition techniques.

Melt Index (MI, also referred to as 12) is measured according to ASTM D1238 at 190° C., under a load of 2.16 kg unless otherwise noted. The units for MI are g/10 min or dg/min.

High Load Melt Index (HLMI, also referred to as 121) is measured according to ASTM D1238 at 190° C., under a load of 21.6 kg unless otherwise noted.

Melt Index Ratio (MIR) is the ratio of the high load melt index to the melt index (I21/I2).

All molecular weights are reported in g/mol unless otherwise noted.

Examples

All manipulations were performed in an inert N₂ purged glove box unless otherwise stated. All anhydrous solvents were purchased from Fisher Chemical and were degassed and dried over molecular sieves prior to use. Deuterated solvents were purchased from Cambridge Isotope Laboratories and dried over molecular sieves prior to use. n-Butyl lithium (2.5 M solution in hexane) was purchased from Sigma-Aldrich. Hafnium tetrachloride (HfCl₄) 99+%, trimethylsilylmethyl trifluoromethanesulfonate was procured from TCI America and used as received. Potassium cyclopentadienide (KCp) was prepared according to the literature procedure. The ¹H NMR measurements were recorded on a 400 MHz Bruker spectrometer.

Synthesis of Trimethylsilylmethylcyclopentadiene, Me₃SiCH₂CpH. A neat trimethylsilylmethyl trifluoromethanesulfonate (25.0 g, 105.8 mmol) was dissolved in 300 mL of diethyl ether and cooled to −25° C., and a solid potassium cyclopentadienide (11.14 g, 106.9 mmol) was slowly added to the mixture over a period of 10 minutes to 15 minutes. The resulting mixture was stirred overnight at room temperature. Insoluble materials were filtered out. Volatiles from the reaction mixture were carefully removed under dynamic vacuum to avoid evaporating the volatile trimethylsilylmethylcyclopentadiene, (Me₃Si)CH₂CpH. The reaction flask (250 mL round bottom flask) and frit with celite were weighted to calculate yield of the product after extraction. The crude materials were then extracted into pentane (3×50 mL) and used without any further purification. Yield: 15.47 g (95.2%). The ¹H NMR spectrum was recorded for the crude material to ensure the product formation. ¹H NMR (400 MHz, C₆D₆): δ−0.05 (9H, s, Si—CH₃), 1.77 (2H, d, J_(HH)=1.2 Hz, Me₃Si—CH₂), 2.83 (1H, sex, J_(HH)=1.5 Hz, Cp-CH), 5.80-6.49 (4H, m, Cp-CH) ppm.

Synthesis of Lithium trimethylsilylmethylcyclopentadienide, Me₃SiCH₂CpLi. An hexane solution of n-butyl lithium (41.5 mL, 103.8 mmol, 2.5 M solution) was added dropwise to a precooled solution (1:1 mixture of pentane and diethyl ether, 200 mL) of Me₃SiCH₂CpH (15.47 g, 101.7 mmol) over a period of 40 minutes to 50 minutes at −25° C. The resulting mixture was gradually brought to room temperature and then continuously stirred overnight. Volatiles were removed in vacuo and remaining crude materials were thoroughly washed with pentane. The final materials were dried under vacuum to obtain a colorless crystalline solid of Me₃SiCH₂CpLi in 13.6 g (84.6%) yield. ¹H NMR (400 MHz, THF-ds): δ−0.09 (9H, s, Si—CH₃), 1.84 (2H, s, Me₃Si—CH₂), 5.36 (2H, t, J_(HH)=2.6 Hz, Cp-CH), 5.47 (2H, t, J_(HH)=2.6 Hz, Cp-CH) ppm.

Synthesis of Bis-(η⁵-trimethylsilylmethylcyclopentadienyl)hafnium dichloride, (Me₃SiCH₂Cp)₂HfCl₂. A solid HfCl₄ (25.0 g, 78 mmol) was slurried in precooled diethyl ether (300 mL) at −25° C. A solid Me₃SiCH₂CpLi (24.75 g, 156 mmol) was added over a period of 20 minutes to 30 minutes. The resulting mixture was stirred overnight at room temperature. All volatiles were removed in vacuo and the crude materials were subsequently extracted into dichloromethane. Solvents were removed under reduced pressure resulted spectroscopically pure (Me₃SiCH₂Cp)₂HfCl₂ as a colorless solid in 31.0 g (72%) yield. ¹H NMR (400 MHz C₆D₆): δ−0.11 (18H, s, SiMe₃-CH₃), 2.18 (4H, s, Me₃Si—CH₂), 5.68 (8H, s, Cp-CH) ppm.

Synthesis of Bis-(η⁵-trimethylsilylmethylcyclopentadienyl)hafnium dibutyl, (Me₃SiCH₂Cp)₂HfBu₂. An ethereal solution of n-BuLi (3.4 mL, 8.4 mmol; 2.5 M solution in hexanes) was added drop wise to a precooled diethyl ether solution of (Me₃SiCH₂Cp)₂HfCl₂ (2.29 g, 4.2 mmol) over a period of 10 minutes to 15 minutes at −25° C. The resulting mixture was stirred 3 hours at room temperature to ensure completion of the reaction. Insoluble materials were filtered through a pad of celite. Volatiles from the filtrate were removed under vacuum. The crude materials were triturated with hexane and then extracted into hexane, followed by solvent removal afforded a colorless semi-crystalline material of (Me₃SiCH₂Cp)₂HfBu₂ in 2.1 g (85.0%) yield. ¹H NMR (400 MHz, C₆D₆): δ 0.02 (18H, s, SiMe₃-CH₃), 0.28-0.24 (4H, m, Hf—CH₂), 1.06 (6H, t, Hf—CH₃), 1.45-1.43 (4H, m, Hf—CH₂), 1.59-1.55 (4H, m, Hf—CH₂), 1.84 (4H, s, Me₃Si—CH₂), 5.57 (4H, t, Cp-CH), 5.63 (4H, t, Cp-CH) ppm.

Synthesis of (η⁵-trimethylsilylmethylcyclopentadienyl) (η⁵-dimethylsilyl(methylene)methylcyclopentadienyl) hafnium butyl, (Me₃SiCH₂Cp) (CpCH₂Si(Me)₂CH₂—)HfBu. (Catalyst 1) The (Me₃SiCH₂Cp)₂HfBu₂ (2.1 g, 3.5 mmol) was dissolved in toluene 50 mL and then heated at 90° C. The reaction progress was monitored via ¹H NMR spectroscopy and was completed to form the tuck-in catalyst compound 1 in 36 hours. Volatiles from the reaction mixture were removed in vacuo and triturated with hexanes. The solvent removal resulted a thick yellow oil of the desired C—H activated product (Me₃SiCH₂Cp) (CpCH₂Si(Me)₂CH₂—)HfBu in 1.61 g (80.6%) yield. ¹H NMR (400 MHz, C₆D₆): δ−1.22 (1H, d, Hf—CH₂ (n-Bu)), −0.02 (3H, s, SiMe₃-CH₃), 0.00 (9H, s, SiMe₃-CH₃), 0.22 (3H, s, SiMe₃-CH₃), 0.25 (2H, d, Hf—CH₂ (—CH₂SiMe₂-)), 0.79 (1H, d, Hf—CH₂ (n-Bu)), 1.06 (3H, t, Hf—CH₃ (n-Bu)), 1.47-1.38 (2H, m, Hf—CH₂ (n-Bu)), 1.63-1.52 (2H, m, Hf—CH₂ (n-Bu)), 1.90-1.82 (3H, m, Me₃Si—CH₂), 2.01 (1H, d, Me₃Si—CH₂), 5.05-5.01 (2H, m, Cp-CH), 5.47-5.44 (1H, m, Cp-CH), 5.53-5.50 (3H, m, Cp-CH), 5.70-5.68 (2H, m, Cp-CH), 6.05-6.03 (1H, m, Cp-CH) ppm.

SMAO-ES70-875: Methylalumoxane treated silica was prepared in a manner according to the following: In a 4 L stirred vessel in a drybox methylalumoxane (MAO, 30 wt % in toluene, approximately 1,000 g) was added along with approximately 2,000 g of toluene. This solution was then stirred at 60 RPM for 5 minutes. Next, approximately 800 g of ES-70-875 silica was added to the vessel. The resulting slurry was then heated at 100° C. and stirred at 120 RPM for 3 hours. The temperature was then reduced to 25° C. and cooled to temperature over 2 hours. Once cooled, the vessel was set to 8 RPM and placed under vacuum for 72 hours. After emptying the vessel and sieving the supported MAO, approximately 1,100 g of supported MAO was collected.

ES-70-875 silica is ES70™ silica (PQ Corporation, Conshohocken, Pa.) that has been calcined at approximately 875° C. Specifically, the ES70™ silica was calcined at 880° C. for 4 hours after being ramped to 880° C. according to the following ramp rates:

° C. ° C./h ° C. ambient 100 200 200 50 300 300 133 400 400 200 800 800 50 880

Supported Catalyst 1 was prepared as follows: (η⁵-trimethylsilylmethylcyclopentadienyl) (η⁵-dimethylsilyl(methylene) methylcyclopentadienyl) hafnium butyl, (Me₃SiCH₂Cp) (CpCH₂Si(Me)₂CH₂—)HfBu. (Catalyst 1) (0.016 g, 30.0 umol) was added to a slurry of 1.0 g SMAO-ES70-875 with 10 mL toluene in a Celestir vessel. This slurry/mixture was stirred for 3 hours and then filtered, washed with toluene (1×10 mL) and then hexane (2×10 mL). The supported catalyst was then dried under vacuum for 18 hours.

Supported Catalyst 2, (bis(1,3-methyl,n-butylcyclopentadienyl)zirconium dichloride activated with MAO and supported on ES 757™ silica, was prepared using a method similar to the preparation described in U.S. Pat. No. 7,579,415.

General Procedure for High Throughput Ethylene/1-Hexene Polymerization and Polymer Characterization (Table 1)

Preparation of catalyst slurry for high throughput run: In a dry box, 45 mg of supported catalyst was weighed into a 20 mL glass vial. 15 mL of toluene was added to the vial to make a slurry that contained 3 mg supported catalyst/mL slurry. The resulting mixture was vortexed prior to injection.

Starting material preparations: Solvents, polymerization grade toluene and isohexane were supplied by ExxonMobil Chemical Company and thoroughly dried and degassed prior to use. Polymerization grade ethylene was used and further purified by passing it through a series of columns: 500 cc Oxyclear cylinder from Labclear (Oakland, Calif.) followed by a 500 cm³ column packed with dried 3 Å mole sieves purchased from Aldrich Chemical Company, and a 500 cm³ column packed with dried 5 Å mole sieves purchased from Aldrich Chemical Company. TnOAl (tri-n-octylaluminum, neat) was used as a 2 mmol/L solution in toluene.

Preparation of catalyst slurry for high throughput run: In a dry box, 45 mg of supported catalyst was weighed into a 20 mL glass vial. 15 mL of toluene was added to the vial to make a slurry that contained 3 mg supported catalyst/mL slurry. The resulting mixture was vortexed prior to injection.

High Throughput—Polymerizations.

Transition metal compounds were supported as detailed in the examples above. Solvents, polymerization grade toluene and isohexane were supplied by ExxonMobil Chemical Company and thoroughly dried and degassed prior to use. Polymerization grade ethylene was used and further purified by passing it through a series of columns: 500 cm³ Oxyclear™ cylinder from Labclear (Oakland, Calif.) followed by a 500 cm³ column packed with dried 3 Å molecular sieves purchased from Aldrich Chemical Company, and a 500 cm³ column packed with dried 5 Å molecular sieves purchased from Aldrich Chemical Company. TnOAl was used as a 2 mmol/L solution in toluene.

Reactor Description and Preparation.

Polymerizations were conducted in an inert atmosphere (N₂) dry box using autoclaves equipped with an external heater for temperature control, glass inserts (internal volume of reactor=22.5 mL), septum inlets, regulated supply of nitrogen, ethylene and hexene, and equipped with disposable PEEK mechanical stirrers (800 RPM). The autoclaves were prepared by purging with dry nitrogen prior to use.

Ethylene/1-Hexene Copolymerization.

The reactor was prepared as described above, and then purged with ethylene. Isohexane, 1-hexene and TnOAl were added via syringe at room temperature and atmospheric pressure. The reactor was then brought at a process temperature (85° C.) and charged with ethylene at a process pressure (130 psig=896 kPa).

Table 1 illustrates the results of polymers having different properties that were obtained by the polymerization of ethylene in the presence of 300 ppm H₂, while stirring at 800 RPM. The transition metal compound (100 μL of a 3 mg/mL toluene slurry, unless indicated otherwise) was added via syringe to the reactor at process conditions. TnOAl was used as 200 μL of a 20 mmol/L in isohexane solution. Ethylene was allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/−2 psig). Reactor temperature was monitored and typically maintained within +/−1° C. Polymerizations were halted by addition of approximately 50 psi O₂/Ar (5 mole % O₂) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations were quenched after a predetermined cumulative amount of ethylene had been added or for a maximum of 45 minutes polymerization time. The final conversion (in psi) of ethylene added/consumed was reported in Table 1, in addition to the quench time for each run. The reactors were cooled and vented. The polymer was isolated after the solvent was removed in vacuo. Polymer Products were characterized using Rapid GPC, Rapid DSC, and FTIR.

Catalyst Compounds represented by Formula (II), such as Catalyst Compound 1, were found to be active catalyst compound for olefin polymerization. Table 1 illustrates controlled ethylene-hexene copolymer composition formation using catalyst systems including Catalyst Compound 1 and SMAO-ES70-875 activator. Furthermore, Catalyst Compound 1 was found to be a good comonomer incorporator, with a 1-hexene comonomer content of about 13 wt %, for example (Run 1). Polymers with lower comonomer content than 13 wt % were also observed, with hexene wt % values from about 2.45 wt % to about 12.9 wt %. By using the Catalyst Compound 1, narrow PDI values were observed (e.g., from 1.99 to 2.64), as compared to the comparative Catalyst Compound 2. Furthermore, by using the Catalyst Compound 1, PDI values increased as the hexene comonomer content in the polymer product increased. Such trend was not observed when using the comparative Catalyst Compound 2 (Table 1, Run 7 to Run 12). Without being bound by theory, the increase of the PDI values as the hexene comonomer content increased when using the Catalyst Compound 1 may result from the tuckin activation and ligand modification as hexene inserted at higher frequency.

As illustrated in Table 1, Catalyst Compound 1 provided high molecular weight polyolefins (e.g., Mw from about 800,000 g/mol to about 2,300,000 g/mol). As the hexene content increased, the Tm decreased (e.g., Run 1 compared to Run 6), with Tm values from about 112° C. to 126° C. Furthermore, higher Mn values, Mw values, Mz values were observed when Catalyst Compound 1 was used for the polymerization process as compared to the comparative Catalyst Compound 2.

TABLE 1 Sup- ported Cata- Mn* Mw* Mz* Run lyst (g/mol) (g/mol) (g/mol) Mw/Mn* 1 1 864,354.9 2,279,275 6,135,757 2.64 2 1 521,035.3 1,342,320 4,453,003 2.58 3 1 531,076.2 1,319,075 4,391,875 2.48 4 1 472,905.3 975,415.9 3,063,327 2.06 5 1 407,345.6 844,957.2 2,233,425 2.07 6 1 410,093.6 814,540.9 2,229,143 1.99 7 2 349,300.3 654,142.1 1,654,357 1.87 8 2 237,947.9 489,774.4 1,144,504 2.06 9 2 308,958.1 526,626.6 1,058,146 1.70 10 2 203,054.7 420,950.9 946,368 2.07 11 2 242,327.1 454,867.2 1,141,283 1.88 12 2 205,606.9 443,283.6 1,149,488 2.16 *Rapid GPC FT-IR Sup- Como- Peak ported nomer Quench Tm Hexene Cata- Content Yield Time (° C.) Charge Run lyst (wt %) (g) (second) 1st Heat (mG) 1 1 12.951 0.028 2,700.11 112.026 201.9 2 1 10.388 0.095 1,081.91 112.184 121.14 3 1 8.937 0.101 1,186.3 112.134 121.14 4 1 4.616 0.092 581.21 121.405 40.38 5 1 4.011 0.093 676.62 121.127 40.38 6 1 2.45 0.089 905.2 126.121 20.19 7 2 7.149 0.032 2,700.4 117.203 201.9 8 2 5.407 0.092 1,483.9 118.615 121.14 9 2 5.603 0.096 1,046.7 118.178 121.14 10 2 2.808 0.087 1,835.5 125.089 40.38 11 2 2.928 0.092 2,010.5 125.077 40.38 12 2 0.913 0.086 2,452.1 129.033 20.19

Polymerization example in autoclave. A 2 Liters Autoclave reactor (Parker Autoclave Engineers Research Systems) was filled with 200-400 grams of granular NaCl. The salt was agitated (100 to 200 RPM of impeller rotation speed) and heated to a temperature above 100° C., under a continuous purge of house nitrogen gas for 60 minutes. Such process reduced the residual oxygen and moisture within the reactor and salt bed. A solid scavenger (4-6 grams, about 7-17 wt % TiBAl supported on ES70™ silica that had been calcined at 100° C.) was loaded into a Whitey sample cylinder and added to the reactor with nitrogen charge. The reactor was adjusted to the desired reactor temperature (85° C.) and at ambient pressure. 21 ssc (scc=standard cubic centimeter) of hydrogen gas was loaded into the reactor using a Brooks Mass Flow Controller. Then 40 mls of iso-pentane at room temperature was added using a Whitey sample cylinder and injected with high pressure nitrogen. Using a ratio control, the comonomer (1-hexene) of 3.99 mls was pushed into the reactor from a syringe pump (Teledyne Isco) while ethylene was filling the reactor to a total pressure of about 240 psig. Solid catalyst was loaded into a small injection tube, under inert atmosphere nitrogen, in a glovebox. The catalyst injection tube was attached to the reactor and catalyst was quickly charged into the reactor with high pressure nitrogen of up to 300 psig-350 psig, and the polymerization was monitored for a reaction time of 60 minutes. Ethylene monomer was continuously added, maintaining a constant total reactor pressure of 300 to 350 psig. The nitrogen was continuously injected to maintain a constant ethylene partial pressure. The comonomer and hydrogen were continuously added and adjusted to maintain a suitable gas phase ratios of comonomer/ethylene and hydrogen/ethylene, as monitored by gas chromatography. After the reaction time described above, the reactor was vented and cooled to ambient pressure and ambient temperature. The reaction product was collected and weighed for an approximate yield. The product was transferred to a standard 4 L beaker with 2,000 mL of distilled water and soap. The solution was rapidly agitated using a magnetic stirring plate and a stir bar for a time of 5 minutes or more. The solution was then transferred to a separator funnel and then allowed to settle. The heavy particles that fell to the bottom of the solution were washed out. The polymer was washed until the remaining water was clear of particles. The polymer was collected by filtration flask, oven dried at 100° C. overnight, and the weight was measured for final isolated yield. Reaction and characterization data are reported in Table 2.

Table 2 reports the Mn, Mw, Mz, Mw/Mn, and g′_((vis)) values as determined by GPC-4D, as well as MI and MIR values of the polyethylene copolymer produced after carrying out the polymerization for 1 hour, at 85° C., using Supported Catalyst Compound 1. The catalyst productivities of Catalyst Compound 1 and Compound 2 are also reported in Table 2. When Catalyst Compound 1 was used for the polymerization, high hexene incorporation was observed with a comonomer content of 10.84 wt %, as well as a high linearity with a g′_(vis) value of 0.967. Furthermore, polymer produced using Catalyst Compound 1 had a broad orthogonal composition distribution, indicating that the majority of the comonomer is incorporated in the high molecular weight (HMW) polymer chain. Also, higher MI value and catalyst productivity value were both observed when Catalyst Compound 1 was used in the polymerization, as compared to the comparative Catalyst Compound 2.

TABLE 2 MI Catalyst Supported (g/ Mn Mw Mz Productivity Hexene Run Catalyst 10 min) MIR (g/mol) (g/mol) (g/mol) (gP/gCat/h) Mw/Mn (wt %) g′_(vis) 1 1 0.82 18.4 29,523 108,812 214,815 4,510 3.88 10.84 0.967 2 2 0.19 20.4 3,304

FIG. 1 is a GPC-4D spectrum of a polyethylene copolymer formed from Catalyst Compound 1. As shown in FIG. 1, a broad orthogonal composition distribution was observed, as the hexene content increased in the high molecular weight portion of the composition, as compared to the hexene content in the low molecular weight portion of the composition.

FIG. 2 is a TREF graph for polymer made with Catalyst Compound 1. As shown in FIG. 2, Catalyst Compound 1 provides a bimodal composition distribution with 80.1% of the low density resin with the peak eluting at 70° C. and the high density portion, 19.8% eluting at 89° C. Without being bound by theory, the BOCD behavior observed by GPC-4D and the bimodality of the composition observed by TREF may be coupled to the increase in PDI as the hexene in the polymer increases.

Overall, catalysts, catalyst systems, and processes of the present disclosure can provide formation of polymers having high molecular weights. Catalysts, catalyst systems, and processes of the present disclosure can further provide polymers having a range of comonomer contents, such as from about 0.05 wt % to about 18 wt %. In particular, the present disclosure can provide new and improved hafnium-containing metallocene catalysts with enhanced molecular weight capability.

The phrases, unless otherwise specified, “consists essentially of” and “consisting essentially of” do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

All documents described herein are incorporated by reference herein, including any priority documents and or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure. 

1. A catalyst compound represented by Formula (I):

wherein: M is a hafnium; each of R¹, R², R³ and R⁴ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or R¹⁶-T²(R¹⁷)₃ wherein R¹⁶ is C₁ to C₄ hydrocarbyl, T² is group 13, 14, 15, or 16 element, and each R¹⁷ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl; each of R⁵, R⁶, R⁷, R⁸, and R⁹ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸-T³(R¹⁹)₃ wherein R¹⁸ is C₁ to C₄ hydrocarbyl, T³ is group 13, 14, 15, or 16 element, and each R¹⁹ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl; X¹ is a univalent anionic ligand; each of R¹⁰ and R¹¹ is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, or R¹⁰ and R¹¹ join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent; R¹² and R¹³ are hydrogen; n is 1, 2, 3, 4, or 5; T¹ is group 13, 14 (carbon excluded), 15, or 16 element; and R¹⁴ and R¹⁵ are independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl.
 2. The catalyst compound of claim 1, wherein T¹ is Si.
 3. The catalyst compound of claim 1, wherein: at least one of R¹, R², R³ and R⁴ is R¹⁶—Si(R¹⁷)₃ wherein R¹⁶ is C₁ to C₄ hydrocarbyl, and each R¹⁷ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl; and at least one of R⁵, R⁶, R⁷, R⁸, and R⁹ is —R¹⁸—Si(R¹⁹)₃ wherein R¹⁸ is C₁ to C₄ hydrocarbyl, and each R¹⁹ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl.
 4. The catalyst compound of claim 1, wherein n is 1 and R¹⁴ and R¹⁵ are methyl.
 5. The catalyst compound of claim 1, wherein each of R¹, R², R³ and R⁴ is independently hydrogen or C₁ to C₄₀ substituted or unsubstituted hydrocarbyl.
 6. The catalyst compound of claim 5, wherein R¹, R², R³ and R⁴ are hydrogen.
 7. The catalyst compound of claim 1, wherein each of R⁵, R⁶, R⁷, R⁸, and R⁹ is independently hydrogen, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸—Si(R¹⁹)₃ wherein R¹⁸ is C₁ to C₄ hydrocarbyl, and each R¹⁹ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl.
 8. The catalyst compound of claim 7, wherein one of R⁵, R⁶, R⁷, R⁸, and R⁹ is —R¹⁸—Si(R¹⁹)₃ where R¹⁸ is C₁ to C₄ hydrocarbyl, each R¹⁹ is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl, and four of R⁵, R⁶, R⁷, R⁸, and R⁹ are hydrogen.
 9. The catalyst compound of claim 7, wherein each R¹⁹ is independently C₁ to C₅ unsubstituted hydrocarbyl.
 10. The catalyst compound of claim 9, wherein R¹⁸ is C₁ and each R¹⁹ is methyl.
 11. The catalyst compound of claim 1, wherein n is 1, and R¹, R², R³, R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ are hydrogen.
 12. The catalyst compound of claim 1, wherein X¹ is selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.
 13. The catalyst compound of claim 12, wherein X¹ is butyl.
 14. The catalyst compound of claim 1, wherein the catalyst compound is one or more of:


15. The catalyst compound of claim 14, wherein the catalyst compound is selected from:

16.-26. (canceled)
 27. An ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one C₃-C₂₀ alpha-olefin, and the catalyst of claim 1 and an activator in at least one gas-phase reactor, the copolymer having an Mw value of from 50,000 to 5,000,000, an Mn value of from 100,000 to 2,000,000, an Mz value of from 500,000 to 10,000,000, an Mw/Mn value of from 1.2 to 10, an MI of from about 0.05 g/10 min to about 100 g/10 min, a MIR value from 12 to 100, a g′_(vis) of greater than 0.9, and a comonomer content of from 0.05 wt % to 18 wt %.
 28. An ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one C₃-C₂₀ alpha-olefin, and the catalyst of claim 1 and an activator in at least one gas-phase reactor, the copolymer having an Mw value of from 500 to 100,000, an Mn value of from 500 to 100,000, an Mz value of from 500 to 500,000, an Mw/Mn value of from 1.2 to 10, an MI of from about 0.05 g/10 min to about 100 g/10 min, a MIR value from 12 to 100, a g′_(vis) of greater than 0.9, and a comonomer content of from 0.05 wt % to 18 wt %.
 29. (canceled)
 30. The ethylene alpha-olefin copolymer of claim 27, wherein the copolymer has a bimodal molecular weight distribution as determined by Gel Permeation Chromatography. 31.-43. (canceled)
 44. A process comprising: heating at a temperature of from about 70° C. to about 120° C. for a time of from about 1 hour to about 72 hours an intermediate compound represented by Formula (II):

wherein M′ is hafnium; each of R^(1′), R^(2′), R^(3′) and R^(4′) is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R^(16′)-T^(2′)(R^(17′))₃ wherein R^(16′) is C₁ to C₄ hydrocarbyl, T^(2′) is group 13, 14, 15, or 16 element, and each R^(17′) is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl; each of R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R^(18′)- T^(3′)(R^(19′))₃ wherein R^(18′) is C₁ to C₄ hydrocarbyl, T^(3′) is group 13, 14, 15, or 16 element, and each R^(19′) is independently C₁ to C₂₀ substituted or unsubstituted hydrocarbyl; each of X^(1′) and X^(2′) is independently a univalent anionic ligand; each of R^(10′) and R^(11′) is independently hydrogen or a C₁ to C₂₀ containing hydrocarbyl or substituted hydrocarbyl, or R^(10′) and R^(11′) join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent; n′ is 1, 2, 3, 4, or 5; T^(1′) is group 13, 14 (carbon excluded), 15, or 16 element; each of R^(14′) and R^(15′) is independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl; and R^(20′) is C₁ or more substituted or unsubstituted hydrocarbyl; and obtaining a catalyst compound represented by Formula (I):

wherein: M is a hafnium; each of R¹, R², R³ and R⁴ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or R¹⁶-T²(R¹⁷)₃ wherein R¹⁶ is C₁ to C₄ hydrocarbyl, T² is group 13, 14, 15, or 16 element, and each R¹⁷ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl; each of R⁵, R⁶, R⁷, R⁸, and R⁹ is independently hydrogen, alkoxide, C₁ to C₄₀ substituted or unsubstituted hydrocarbyl, or —R¹⁸-T³(R¹⁹)₃ wherein R¹⁸ is C₁ to C₄ hydrocarbyl, T³ is group 13, 14, 15, or 16 element, and each R¹⁹ is independently C₁ to C₅ substituted or unsubstituted hydrocarbyl; X¹ is a univalent anionic ligand; each of R¹⁰ and R¹¹ is independently hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, or R¹⁰ and R¹¹ join to form a substituted or unsubstituted, saturated, partially unsaturated, cyclic or polycyclic substituent; R¹² and R¹³ are hydrogen; n is 1, 2, 3, 4, or 5; T¹ is group 13, 14 (carbon excluded), 15, or 16 element; and R¹⁴ and R¹⁵ are independently C₁ to C₄₀ substituted or unsubstituted hydrocarbyl.
 45. The process of claim 44, wherein the heating comprises heating the intermediate compound represented by Formula (II) at a temperature of from about 85° C. to about 95° C. for a time of from about 30 hours to about 40 hours. 